1,4-Disubstituted benzenes as insecticides

ABSTRACT

Compounds of formula I:  
                 
 
     wherein A, B, D, and R are as defined herein and their agriculturally acceptable salts are disclosed as effective insecticides. In addition, compositions comprising an insecticidally effective amount of a compound of Formula I in admixture with at least one agriculturally acceptable extender or adjuvant and methods of controlling insects comprising applying said compositions to locus on crops where control is desired are disclosed. It is emphasized that his abstract is provided to comply with the rules requiring an abstract that will allow a searcher or other reader to quickly ascertain the subject matter of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims (see 37 C.F.R. 1.72(b)).

[0001] This is a nonprovisional of Application Nos. 60/229,701 and60/277,203 filed on Sep. 1, 2000 and Mar. 20, 2001, respectively.

FIELD OF THE INVENTION

[0002] The present invention relates to methods for controlling insects.In particular, it relates to control by the application of certain novelsubstituted benzenes.

BACKGROUND OF THE INVENTION

[0003] The present invention relates to methods for controlling insects.In particular, it relates to control by the application of certain novelsubstituted benzenes. More particularly, it pertains to1,4-disubstituted benzene compounds and compositions containing the samewhich are useful for controlling insects in agricultural crops. Evenmore particularly, this invention relates 1,4-disubstituted benzenecompounds and compositions and their uses as insecticides against avariety of insects, including larvae, such as tobacco budworm.

SUMMARY OF THE INVENTION

[0004] It has now been found that certain substituted benzenes,particularly 1,4-disubstituted benzenes, and their agriculturallyacceptable salts, are effective as insecticides. These benzenes may berepresented by the following formula I:

[0005] in which:

[0006] A is hydrogen; aryl; alkylheterocyclyl; alkenylaminopolycyclyl;alkenylaminoheterocyclyl; alkylaminopolycyclyl; carbonylaminopolycyclyl;and Formula III, where Formula III is

—(CH₂)_(n)—U—R²

III

[0007] where

[0008] n is 0 or 1;

[0009] U is —CH₂—, —O—CH₂—, oxygen, sulfur, sulfonyl, alkyl,oxyalkyloxy, alkenylamino, cabonylamino and —NR⁵, where R⁵ is hydrogen,hydroxy, alkyl, haloalkyl, sulfonylalkyl, cabonylamino, andcarbonylalkyl;

[0010] R² is aryl; alkylpolycyclyl; heterocyclyl; polycyclyl; 1-R³;1-R⁴; and 2-R⁴, where:

[0011] R³ is

[0012] where J, L, and W are independently hydrogen, halogen, cyano,nitro, ammo, carboxyl, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy,aminoalkoxy, nitrilyl, carbonyl, alkylcarbonyl, haloalkylcarbonyl,alkoxycarbonyl, haloalkoxycarbonyl, aryl, aryloxy, and heterocyclyl;

[0013] R⁴ is

[0014] where X, Y, and Z are independently hydrogen, halogen, cyano,nitro, amino, azido, carboxyl, alkyl, alkynyl, haloaLkyl, haloalkylthio,nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl,haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenyl, aryl,aryloxy, and heterocyclyl;

[0015] B and D are independently hydrogen, halogen, alkyl, haloalkyl,alkoxy, haloalkoxy, alkoxyaminoalkyl, 2-(Formula III), 3-(Formula III),5-(Formula III), and 6-(Formula III), where Formula III, n, U, R², R³,R⁴, R⁵, J, L, W, X, Y, and Z are as defined above;

[0016] R is —T—(CH₂)_(m)—R¹, —N(R⁶)(R⁷) or heterocyclyl;

[0017] T is —CH₂—, carbonyl, oxygen, nitrogen, and sulfur;

[0018] m is 0, 1, 2, 3, or 4;

[0019] R¹ is —N(R⁸)(R); alkyl; aryl; —C(O)N(R¹²)(R¹³); oxyalkyl;haloalkyl; heterocyclyl; cycloalkyl; —N(O)(R¹⁴)(R¹⁵); —P(O)(R¹⁴)(R¹⁵);—P(S)(R¹⁴)(R¹⁵); alkylamino, where the cyclohexyl, aryl and heterocyclylmoieties may be optionally substituted with halogen, hydroxy, alkyl,haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl,alkylamino; where

[0020] R⁶, R⁷, R⁸, R⁹, R¹², R¹³, R¹⁴ and R¹⁵ are independently hydrogen,alkyl, alkoxy, alkylthio, acetyl, alkoxycarbonyl, alkoxyalkyl,aminoalkyl, carbonylamino, and —(CH₂)_(p)—N(R⁶)(R⁷), where

[0021] p is 1 or2; and

[0022] R¹⁶ and R¹⁷ are independently hydrogen, alkyl, alkoxy,alkoxyalkyl, and aminoalkyl.

[0023] The present invention is also directed to a compositioncontaining an insecticidally effective amount of a compound of Formula Iin admixture with at least one agriculturally acceptable extender oradjuvant, wherein A, B, D, and R are as defined above.

[0024] In addition, the present invention relates to a method ofcontrolling insects that comprises applying to locus on crops, such ascotton, vegetables, fruits, where control is desired an insecticidallyeffective amount of a the above composition.

DETAILED DESCRIPTION OF THE INVENTION

[0025] In one aspect of the present invention, certain substitutedbenzenes, particularly 1,4-disubstituted benzenes, and theagriculturally acceptable salts thereof, have now been found to beeffective as insecticides. These benzenes may be represented by thefollowing formula I:

[0026] in which:

[0027] A is selected from the group consisting of hydrogen; aryl;alkylheterocyclyl; alkenylaminopolycyclyl; alkenylaminoheterocyclyl;alkylaminopolycyclyl; carbonylaminopolycyclyl; where the aryl,heterocyclyl and polycyclyl moieties are optionally substituted with oneor more of the following: halogen, cyano, nitro, amino, carboxyl, allyl,haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl,haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; andFormula III, where Formula III is

—(CH₂)_(n)—U—R²

III

[0028] wherein

[0029] n is 0 or 1;

[0030] U is selected from the group consisting of —CH₂—, —O—CH₂—,oxygen, sulfur, sulfonyl, alkyl, oxyalkyloxy, alkenylamino, cabonylaminoand —NR⁵, where R⁵ is selected from the group consisting of hydrogen,hydroxy, alkyl, haloalkyl, sulfonylalkyl, cabonylamino, andcarbonylalkyl;

[0031] R² is selected from aryl; alkylpolycyclyl; heterocyclyl;polycyclyl; where the aryl, heterocyclyl and polycyclyl moieties areoptionally substituted with one or more of the following: halogen,cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy,carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, or aryl; 1-R³; 1-R⁴; and 2-R⁴, wherein:

[0032] R³is

 R³

[0033] where J, L, and W are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl,haloalkyl, alkenyl, alkoxy, haloalkoxy, aminoalkoxy, nitrilyl, carbonyl,allylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl,aryl, aryloxy, and heterocyclyl, where the aryl and heterocyclylmoieties may be optionally substituted with halogen, alkyl, haloalkyl,alkoxy, or haloalkoxy;

[0034] R⁴ is

[0035] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, aryloxy, and heterocyclyl, where thephenyl, aryl, and heterocyclyl moieties may be optionally substitutedwith halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy;

[0036] B and D are independently selected from hydrogen, halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalkyl, 2-(Formula III),3-(Formula III), 5-(Formula III), and 6-(Formula III), wherein FormulaIII, n, U, R², R³, R⁴, R⁵, J, L, W, X, Y, and Z are as defined above;

[0037] R is —T—(CH₂)_(m)—R¹, —N(⁶)(R⁷) or heterocyclyl, where theheterocyclyl moiety may be optionally substituted with halogen, hydroxy,alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, alkylaaa,arylcarbonyl, benzyl, allyl, propargyl, alkylamino; where the arylmoiety may be optionally substituted with halogen, hydroxy, alkyl,haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl

[0038] T is selected from the group consisting of —CH₂—, carbonyl,oxygen, nitrogen, and sulfur;

[0039] m is 0, 1, 2, 3, or 4;

[0040] R¹ is selected from the group consisting of —N(R⁸)(R⁹); alkyl;aryl; —C(O)N(R¹²)(R¹³); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl;—N(O)(R¹⁴)(R¹⁵); —P(O)(R¹⁴)(R¹⁵); —P(S)(R¹⁴)(R¹⁵); alkylamino, where thecycloalkyl, aryl and heterocyclyl moieties may be optionally substitutedwith halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy,alkoxycarbonyl, aryl, arylcarbonyl, alkylamino; where

[0041] R⁶, R⁷, R⁸, R⁹, R¹², R¹³, R¹⁴ and R¹⁵ are independently selectedfrom the group consisting of hydrogen, alkyl, alkoxy, alkylthio, acetyl,alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and—(CH₂)_(p)—N(R¹⁶)(R¹⁷), where

[0042] p is 1 or 2;

[0043] R¹⁶ and R¹⁷ are independently selected from the group consistingof hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl.

[0044] Agriculturally acceptable salts of the 1,4-disubstituted benzenesinclude, but are not limited to, for example, the salts of hydrochloricacid, sulfonic acid, ethanesulfonic acid, trifluoroacetic acid,methylbenzenesulfonic acid, phosphoric acid, gluconic, acid, and pamoicacid.

[0045] Some preferred compounds are those in which A is selected fromthe group consisting of hydrogen; alkylaminopolycyclyl;carbonylaminopolycyclyl; where the polycyclyl moieties are optionallysubstituted with one or more of the following: halogen, cyano, nitro,amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl,alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, oraryl; and Formula III, where Formula IIII is

—(CH₂)_(n)U—R²

III

[0046] wherein

[0047] n is 0 or 1;

[0048] U is selected from the group consisting of —CH₂—, oxygen, and—NR⁵, where R⁵ is selected from the group consisting of hydrogen,hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

[0049] R² is selected from aryl, alkylpolycyclyl; heterocyclyl;polycyclyl; where the aryl, heterocyclyl and polycyclyl moieties areoptionally substituted with one or more of the following: halogen,cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy,carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, or aryl; and 1-R³, wherein R³ is:

[0050] where J, L, and W are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl,haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl,alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl,aryl, and aryloxy, where the aryl moieties may be optionally substitutedwith halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;

[0051] B and D are independently selected from hydrogen, halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalkyl;

[0052] R is —T—(CH₂)_(m)—R¹, where

[0053] T is selected from the group consisting of —CH₂—, oxygen,nitrogen, and sulfur;

[0054] m is 1, 2, 3, or 4;

[0055] R¹ is —N(R⁸)(R⁹), where

[0056] R⁸ and R⁹ are independently selected from the group consisting ofhydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl,aminoalkyl, carbonylamino, and —(CH₂)_(p)—N(R¹⁶)(R¹⁷), where

[0057] p is 1 or 2;

[0058] R¹⁶ and R¹⁷ are independently selected from the group consistingof hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and thecorresponding agriculturally acceptable salts thereof.

[0059] Some particularly preferred compounds are those in which A ishydrogen or Formula III, where Formula III is

—(CH₂)_(n)—U—R²

III

[0060] wherein

[0061] n is 0 or 1;

[0062] U is selected from the group consisting of —CH₂—, oxygen, and 13NR⁵, where R⁵ is selected from the group consisting of hydrogen,hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

[0063] R² is selected from heterocyclyl; polycyclyl; where theheterocyclyl and polycyclyl moieties are optionally substituted with oneor more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl,haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl,haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and1-R³, wherein R³ is:

[0064] where J, L, and W are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl,haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl,alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl,aryl, and aryloxy, where the aryl moieties may be optionally substitutedwith halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;

[0065] B and D are independently selected from hydrogen, halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalkyl;

[0066] T is oxygen or nitrogen

[0067] m is 2, 3, or 4;

[0068] R¹ is —N(R⁸)(R⁹), where

[0069] R⁸ and R⁹ are independently selected from the group consisting ofhydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl,aminoalkyl, carbonylamino, and —(CH₂)_(p)—N(R¹⁶)(R¹⁷), where

[0070] p is 1 or 2;

[0071] R¹⁶ and R¹⁷ are independently selected from the group consistingof hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl.

[0072] Some more particularly preferred compounds are those in which Ais Formula III, where Formula III is

—(CH₂)_(n)—U—R²

III

[0073] wherein

[0074] n is 1;

[0075] U is oxygen or —NR⁵, where R⁵ is selected from the groupconsisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, andcarbonylalkyl;

[0076] R² is 1-R³, wherein R³ is:

[0077] where J, L, and W are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl,haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl,alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl,aryl, and aryloxy, where the aryl moieties may be optionally substitutedwith halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;

[0078] B and D are independently selected from hydrogen, halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, alkoxyaminoalkyl;

[0079] T is oxygen or nitrogen

[0080] m is 2;

[0081] R¹ is —N(R⁸)(R⁹), where

[0082] R⁸ and R⁹ are independently selected from the group consisting ofhydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl,aminoalkyl, carbonylamino, and —(CH₂)_(p)—N(R¹⁶)(R¹⁷), where

[0083] p is 1 or 2;

[0084] R¹⁶ and R¹⁷ are independently selected from the group consistingof hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl;

[0085] Some yet even more particularly preferred compounds are those inwhich

[0086] U is oxygen or —NR⁵, where R⁵ is selected from the groupconsisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, andcarbonylalkyl;

[0087] R² is 1-R³, wherein R³ is:

[0088] where J, L, and W are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl,haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl,alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl,aryl, and aryloxy, where the aryl moieties may be optionally substitutedwith halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;

[0089] B and D are independently selected from hydrogen, halogen, andalkoxy;

[0090] T is oxygen;

[0091] R¹ is —N(R⁸)(R⁹); where

[0092] R⁸ and R⁹ are independently selected from the group consisting ofhydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl,aminoalkyl, carbonylamino, and —(CH₂)_(p)—N(R¹⁶)(R¹⁷), where

[0093] p is 1 or 2;

[0094] R¹⁶ and R¹⁷ are independently selected from the group consistingof hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl;

[0095] Some still yet even more particularly preferred compounds arethose in which U is oxygen or —NR⁵, where R⁵ is hydrogen; R² is 1-R³,wherein R³ is:

[0096] where J, L, and W are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl,haloalkyl, alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl,alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl,aryl, and aryloxy, where the aryl moieties may be optionally substitutedwith halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy;

[0097] B and D are hydrogen;

[0098] R¹ is —N(⁸)(R⁹); where R⁸and R⁹ are alkyl.

[0099] In another aspect, the present invention is directed to certainnovel 1,4-disubstituted benzenes per se and agriculturally acceptablesalts thereof falling within the scope of formula I above. Thesecompounds include, for example, the following novel 1,4-disubstitutedbenzenes:

[0100] in which:

[0101] A is Formula III, where Formula III is

—(CH₂)_(n)—U—R²

III

[0102] wherein

[0103] n is 1;

[0104] U is oxygen;

[0105] R² is 1-R³; wherein:

[0106] R³ is

[0107] where J is 2-chloro or 2-fluoro, L is 3-chloro or 5-fluoro, and Wis hydrogen or 4-chloro.

[0108] B and D are hydrogen;

[0109] R is —T—(CH₂)_(m)—R¹, where

[0110] T is oxygen;

[0111] m is 2;

[0112] R¹ is —N(R⁸)(R⁹), where R⁸ and R⁹ are ethyl.

[0113] Additional preferred compounds are those in which A is selectedfrom the group consisting of hydrogen; alkylaminopolycyclyl; andcarbonylaminopolycyclyl; where the polycyclyl moieties are optionallysubstituted with one or more of the following: halogen, cyano, nitro,amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl,alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, oraryl; and Formula III, where Formula III is

—(CH₂)_(n)—U—R²

III

[0114] wherein

[0115] n is 0 or 1;

[0116] U is selected from the group consisting of —CH₂—, oxygen, alkyl,oxyalkyloxy, alkenylamino, cabonylamino and 13 NR⁵, where R⁵ is selectedfrom the group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl,cabonylamino, and carbonylalkyl;

[0117] R² is selected from aryl; alkylpolycyclyl; heterocyclyl;polycyclyl; where the aryl, heterocyclyl and polycyclyl moieties areoptionally substituted with one or more of the following: halogen,cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy,carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, or aryl; and 1-R⁴, wherein R⁴ is

[0118] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy;

[0119] B and D are independently selected from hydrogen, halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, and alkoxyaminoalkyl;

[0120] R is —T—(CH₂)_(m)—R¹ or heterocyclyl; where the heterocyclylmoiety may be optionally substituted with halogen, alkyl, haloalkyl,alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl,propargyl;

[0121] T is selected from the group consisting of —CH₂—, oxygen,nitrogen, and sulfur;

[0122] m is 1, 2, 3, or 4;

[0123] R¹ is selected from the group consisting of —N(R⁸)(R⁹); alkyl;aryl; —C(O)N(R¹²)(R¹³); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl;and —N(O)(R¹⁴)(R¹⁵), where the aryl and heterocyclyl moieties may beoptionally substituted with halogen, alkyl, haloalkyl, alkoxy,haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl; where

[0124] R⁸, R⁹, R¹², R¹³, R¹⁴ and R¹⁵ are independently selected from thegroup consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl,alkoxyalkyl, aminoalkyl, carbonylamino, and —(CH₂)_(p)—N(R¹⁶)(R¹⁷),where

[0125] p is 1 or 2;

[0126] R¹⁶ and R¹⁷ are independently selected from the group consistingof hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and thecorresponding agriculturally acceptable salts thereof.

[0127] Additional particularly preferred compounds are those in which Ais hydrogen or Formula III, where Formula III is

—(CH₂)_(n)—U—R²

III

[0128] wherein

[0129] n is 0 or 1;

[0130] U is selected from the group consisting of —CH₂—, oxygen, and 13NR⁵, where R⁵ is selected from the group consisting of hydrogen,hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl;

[0131] R² is selected from alkylpolycyclyl; heterocyclyl; polycyclyl;where the heterocyclyl and polycyclyl moieties are optionallysubstituted with one or more of the following: halogen, cyano, nitro,amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl,alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, oraryl; and 1-R⁴, wherein R⁴ is

[0132] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy;

[0133] B and D are independently selected from hydrogen, halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, and alkoxyaminoalkyl;

[0134] R is —T—(CH₂)_(m)—R¹ or heterocyclyl; where the heterocyclylmoiety may be optionally substituted with halogen, alkyl, haloalkyl,alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl,propargyl;

[0135] T is selected from the group consisting of oxygen, nitrogen, andsulfur;

[0136] m is 1, 2, 3, or 4;

[0137] R¹ is selected from the group consisting of —N(R⁸)(R⁹); alkyl;aryl; —C(O)N(R¹²)(R¹³); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl;and —N(O)(R¹⁴)(R¹⁵), where the aryl and heterocyclyl moieties may beoptionally substituted with halogen, alkyl, haloalkyl, alkoxy,haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl; where

[0138] R⁸, R⁹, R¹⁰, R¹³, R¹⁴ and R¹⁵ are independently selected from thegroup consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl,alkoxyalkyl, aminoalkyl, carbonylamino, and —(CH)_(p)—N(R¹⁶)(R¹⁷), where

[0139] p is 1 or 2;

[0140] R¹⁶ and R¹⁷ are independently selected from the group consistingof hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and thecorresponding agriculturally acceptable salts thereof.

[0141] Additional more particularly preferred compounds are those inwhich A is Formula III, where Formula III is

—(CH₂)_(n)—U—R²

III

[0142] wherein

[0143] n is 1;

[0144] U is oxygen or 13 NR⁵, where R⁵ is selected from the groupconsisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, andcarbonylalkyl;

[0145] R² is 1-R⁴, wherein R⁴ is

[0146] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy;

[0147] B and D are independently selected from hydrogen, halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, and alkoxyaminoalkyl;

[0148] R is —T—(CH₂)_(m)—R¹ or heterocyclyl; where the heterocyclylmoiety may be optionally substituted with halogen, alkyl, haloalkyl,alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl,propargyl;

[0149] T is oxygen or nitrogen;

[0150] m is 1, 2, 3, or 4;

[0151] R¹ is selected from the group consisting of —N(R⁸)(R⁹); alkyl;aryl; —C(O)N(R¹²)(R¹³); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl;and —N(O)(R¹⁴)(R¹⁵), where the aryl and heterocyclyl moieties may beoptionally substituted with halogen, alkyl, haloalkyl, alkoxy,haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl; where

[0152] R⁸, R⁹, R², R¹³, R¹⁴ and R¹⁵ are independently selected from thegroup consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl,alkoxyalkyl, aminoalkyl, carbonylamino, and —(CH₂)_(p)—N(R¹⁶)(R¹⁷),where

[0153] p is 1 or 2;

[0154] R¹⁶ and R¹⁷ are independently selected from the group consistingof hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and thecorresponding agriculturally acceptable salts thereof.

[0155] Additional yet even more particularly preferred compounds arethose in which A is Formula III, where Formula III is

—(CH₂)_(n)—U—R²

III

[0156] wherein

[0157] U is oxygen or 13 NR⁵, where R⁵ is hydrogen;

[0158] R² is 1-R⁴, wherein R⁴ is

[0159] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy;

[0160] B and D are independently selected from hydrogen, halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, and alkoxyaminoalkyl;

[0161] R is —T—(CH₂)_(m)—R¹ or heterocyclyl; where the heterocyclylmoiety may be optionally substituted with halogen, alkyl, haloalkyl,alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl,propargyl;

[0162] T is oxygen or nitrogen;

[0163] m is 2;

[0164] R¹ is —N(R⁸)(R⁹) or —N(O)(R⁴)(R⁵), where R⁸, R⁹, R¹⁴, and R¹⁵ areindependently selected from the group consisting of hydrogen, alkyl,alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino,and —(CH₂)_(p)—N(R¹⁶)(R¹⁷), where

[0165] p is 1 or 2;

[0166] R¹⁶ and R¹⁷ are independently selected from the group consistingof hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and thecorresponding agriculturally acceptable salts thereof.

[0167] Additional still yet even more particularly preferred compoundsare those in which A is Formula III, where Formula III is

—(CH₂)_(n)—U—R²

III

[0168] wherein

[0169] U is O or 13 NR⁵, where R⁵ is hydrogen;

[0170] R² is selected from 1-R⁴, wherein R⁴ is

[0171] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy;

[0172] B and D are hydrogen;

[0173] the heterocyclyl is a piperazinyl moiety, where the thepiperazinyl moiety may be optionally substituted with halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl,benzyl, allyl, propargyl;

[0174] T is oxygen;

[0175] R¹ is —N(⁸)(⁹) or —N(O)(R¹⁴)(R¹⁵), where R⁸, R⁹, R¹⁴, and R¹⁵ areindependently selected from the group consisting of hydrogen, alkyl,alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, andcarbonylamino; and the corresponding agriculturally acceptable saltsthereof.

[0176] Further preferred compounds are those in which A is Formula III,where Formula III is

—(CH₂)_(n)—U—R²

III

[0177] wherein

[0178] U is O;

[0179] R² is selected from 1-R⁴, wherein R⁴ is

[0180] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,allyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy;

[0181] R¹ is —N(R⁸)(R⁹) or —N(O)(R¹⁴)(R¹⁵), where R⁸, R⁹, R¹⁴ and R¹⁵are alkyl; and the corresponding agriculturally acceptable saltsthereof.

[0182] In addition to those compounds set forth above, the presentinvention is also directed to certain novel 1,4-disubstituted benzenesper se and agriculturally acceptable salts thereof falling within thescope of formula I above. These compounds include, for example, thefollowing novel 1,4-disubstituted benzenes:

[0183] in which:

[0184] A is Formula III, where Formula III is

—(CH₂)_(n)—U—R²

III

[0185] wherein

[0186] n is 1;

[0187] U is oxygen;.

[0188] R² is 1-R⁴; wherein:

[0189] R⁴ is

[0190] where X is 4-chloro or 5-chloro, Y is 6-chloro or 6-bromo, and Zis hydrogen;

[0191] B and D are hydrogen;

[0192] R is —T—(CH₂)_(m)—R¹ or a piperazinyl moiety; where thepiperazinyl moiety is substituted with 4-ethyl;

[0193] T is oxygen;

[0194] m is 2;

[0195] R¹ is —N(R⁸)(R⁹) or —N(O)(R¹⁴)(R¹⁵), where R⁸, R⁹, R¹⁴ and R¹⁵are ethyl; and the agriculturally acceptable salts thereof, preferablythe hydrochloride salts.

[0196] In another aspect, the present invention is directed to acomposition containing an insecticidally effective amount of a compoundof Formula I, including, without limitation, those compounds disclosedabove as being preferred, particularly preferred, and per se novel, inadmixture with at least one agriculturally acceptable extender oradjuvant, wherein A, B, D, and R are as defined above.

[0197] In another aspect, the present invention relates to a method ofcontrolling insects that comprises applying to locus on crops, such ascotton, vegetables, fruits, where control is desired an insecticidallyeffective amount of the above compositions.

[0198] Certain intermediates or the present invention are novel. Theseinclude compounds of formula XII:

[0199] wherein:

[0200] A is —(CH₂)_(n)—U—R²

[0201] wherein

[0202] n is 0 or 1;

[0203] U is —C(O)—, —CH₂—, oxygen, or 13 NR⁵, where R⁵ is selected fromthe group consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl,cabonylamino, and carbonylalkyl;

[0204] R² is selected from hydrogen, halo, hydroxy, and 1-R⁴, wherein:

[0205] R⁴ is

[0206] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy;

[0207] R is —T—(CH₂)_(m)—R¹, where

[0208] T is selected from the group consisting of oxygen, nitrogen, andsulfur;

[0209] m is 0, 1, 2, 3, or 4;

[0210] R¹ is hydrogen, halo, alkyl, or —N(R⁸)(R⁹); where R⁸ and R⁹ areindependently selected from the group consisting of hydrogen, alkyl,alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino,and —(CH)_(p)—N(R¹⁶)(R¹⁷), where

[0211] p is 1 or 2;

[0212] R¹⁶ and R¹⁷ are independently selected from the group consistingof hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl.

[0213] Some preferred intermediates are those in which n is 1; U isoxygen; R² is 1-R⁴, wherein:

[0214] R⁴ is

[0215] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy;

[0216] T is oxygen or sulfur;

[0217] m is 2; and

[0218] R¹ is halo.

[0219] Some particularly preferred intermediates are those in which n is1; U is —CH₂—; R² is 1-R⁴, wherein:

[0220] R⁴ is

[0221] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy;

[0222] T is oxygen;

[0223] m is 0; and

[0224] R¹ is hydrogen or alkyl.

[0225] Additional preferred intermediates are those in which n is 0; Uis —C(O) or —CH₂—; R² is hydrogen, halo or hydroxy; T is oxygen; m is 2;and R¹ is —N(R⁸)(R⁹), where R⁸ and R⁹ are alkyl.

[0226] Additional novel intermediates are compounds of formula UU:

[0227] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloaLkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy; T is selected from the groupconsisting of oxygen, nitrogen, and sulfur; and R¹⁸ is alkyl.

[0228] For the purposes of this invention, as regards to the abovesubstituents, the following definitions apply:

[0229] The terms “alkyl” and “alkoxy”, alone or as part of a largermoiety, include chains of 1 to 14 carbon atoms, preferably straight orbranched alkyls of 1 to 6 carbon atoms; while “halogen” or “halo”, aloneor as part of a larger moiety, includes chlorine, bromine, fluorine, andiodine atoms. The terms “alkenyl” or “alkynyl”, used alone or as part ofa larger moiety, includes straight or branched chains of at least twocarbon atoms containing at least one carbon-carbon double or triplebond, preferably upto 12 carbon atoms, more preferably, up to ten carbonatoms, most preferably up to seven c carbon atoms. The term “cycloalkyl”includes rings of three to twelve carbon atoms, preferably rings ofthree to six carbon atoms. The terms “haloalkyl” and “haloalkoxy”, aloneor as part of a larger moiety, include straight or branched chain alkylsof 1 to 14 carbon atoms, preferably lower straight or branched chainalkyls of 1 to 6 carbon atoms, wherein one or more hydrogen atoms havebeen replaced with halogen atoms, as, for example, trifluoromethyl or2,2,2-trifluoroethoxy, respectively. “Aryl” refers to an aromatic ringstructure, including fused rings, having 5 to 10 carbon atoms.“Heterocyclyl” refers to an aromatic ring structure, including fusedrings, having at least one nitrogen, sulfur or oxygen atom. “Amino”refers to compounds of nitrogen that may be considered derived fromammonia and includes primary, secondary and tertiary amines wherein oneor more of the hydrogen atoms is replaced with alkyl groups. “THF”refers to tetrahydrofuran, “DMF” refers to N,N-dimethylformamide, “DPAD”refers to 1,1′-(azodicarbonyl)dipiperidine, and “A.T.” refers to ambienttemperature.

[0230] The compounds of the present invention were prepared by methodsgenerally known to those skilled in the art. Many of the compounds ofthe present invention in which R¹ is naphthyl were prepared in themanner shown in Schema 1. In Schema 1, a 4-hydroxy-benzaldehyde (SM1)was reacted with the appropriately substituted alkyl chloridehydrochloride salt (SM2) in a solvent, for example, DMF or THF, at 0° C.to ambient temperature in the presence of a base, for example, potassiumcarbonate, to yield the appropriately substituted alkoxy benzaldehyde(BB). The appropriately substituted benzaldehyde (BB) was then reducedin a solvent, for example methanol, with a reducing agent, for example,lithium aluminum hydride, sodium borohydride, or triacetoxyborohydride,to yield the appropriately substituted phenyl alkoxy alcohol (CC). Theappropriately substituted phenyl alkoxy alcohol (CC) can also beprepared by reacting the appropriately substituted alkyl chloridehydrochloride salt (SNU) with either the appropriately substituted acid(SM3) or phenyl alcohol (SM4) in a solvent in the presence of a reducingagent as set forth above. The appropriately substituted phenyl alkoxyalcohol (CC) can then be reacted with either p-toluene sulfonyl chloride(SM5) and a base, for example triethylamine, in a solvent to form theappropriately substituted phenyl alkylthio- or alkoxysulfonyl toluene(DD) or sulfonyl chloride in a solvent to form the appropriatelysubstituted phenylalkylthio or phenylalkoxy chloride hydrochloride (EE).

[0231] If necessary, the naphthyl ring can be prepared at this time. Ingeneral, the naphthyl ring was prepared via the formation of theappropriate naphthol. The preparation of the naphthol begins byreacting: 1) the appropriately substituted benzaldehyde (SM6) witheither sodium hydride and 3-(triphenylphosphino)propanoate hydrochloridein THF and N-N-dimethylsulfoxide (DMF) or with succinic acid, disodiumsalt and acetic anhydride to form the appropriately substitutedphenylbutenoic acid (FF); 2) the appropriately substituted phenyl iodide(SM7) with but-3-ynol, a base, for example, triethylamine, copper iodideand a palladium phosphine complex to yield the appropriately substitutedphenylbutynol (GG); 3) the appropriately substitutedphenylcarbonylpropanoic acid (SM8) with zinc and mercury (II) chloridein water to form the appropriately substituted phenylbutanoic acid (HH),which can also be preprepared by hydrogenating the appropriatelysubstituted phenylbutenoic acid (FF) or phenylbutynol (GG) in alcoholwith palladium on carbon followed by treatment with chromium oxide andsulfuric acid; 4) the appropriately substituted2-(diethylaminocarbonyl)benzene (SM9) with n-butyllithium followed byprop-2-enylbromide and a dimethylthio-copper chloride complex to yieldthe appropriately substituted2-(diethylaminocarbonyl)-3-prop-2-enylbenzene (JJ); or 5) theappropriately substituted benzene (SM10) with oxolan-2-one and aluminiumchloride at elevated temperature to form the appropriately substitutedtrihydronaphthalen-1-one (KK). The trihydronaphthalen-1-one (KK) canalso be prepared by reacting the appropriately substitutedphenylbutanoic acid (HH) with an acid, for example polyphosphoric acid,or reacting the appropriately substituted2-(diethylaminocarbonyl)-3-prop-2-enylbenzene (JJ) with methyllithium.The appropriately substituted trihydronaphthalen-1-one (KK) is thenreacted with bromine in a solvent, for example methylene chloride, toform the the appropriately substituted 2-bromo-trihydronaphthalen-1-one(LL). The appropriately substituted 2-bromo-trihydronaphthalen-1-one(LL) is then reduced with a reducing agent and lithiumbromide in asolvent, for example, DMF, in the manner described above to form theappropriately substituted naphthol (MM), which is commercially availabewhen (MM) is 4-chloronaphthol. The appropriately. substiuted naphthol(MM) was then reacted with either the appropriately substitutedbenzaldehyde (BB), alcohol (CC), toluene (DD), or hydrochloride (EE) toform the targeted 1-substitutedalkylthio or alkoxy-4-((substitutednaphth-1-yl)oxyalkyl)benzene (I), for example,(2-(4-(((4-chloronaphthyl)methoxy)methyl)phenoxy)ethyl)diethylamine.

[0232] Additional substituents can be added to the naphthol ring byreacting a 6-aminonaphth-1-ol (SM11) with toluene sulfonyl chloride inthe manner disclosed above to yield the6-amino-1-(methylphenylsulfonyloxy)naphthalene (NN). The6-amino-1-(methylphenylsulfonyloxy)naphthalene (NN) was then reactedwith t-butyl nitrite in a solvent, for example at 0° C. followed by acopper (II) halide, for example, copper (II) chloride, to yield theappropriate 6-halo-1-(methylphenylsulfonyloxy)naphthalene (PP). The6-amino-1-(methylphenylsulfonyloxy)naphthalene (NN) was also reactedwith an excess of a copper (II) halide, for example, copper (II)chloride, in a solvent followed by t-butylnitrite in the mannerdisclosed above to form the appropriate5,6-dihalo-1-(methylphenylsulfonyloxy)naphthalene (QQ). Theappropriately substituted naphthalene (QQ) or (PP) can then reacted witha base, for example, potassium hydroxide, and an alcohol, for example,ethanol, in a mixture of a solvent, for example, THF, and water to yieldthe appropriately substituted. naphthol (RR), for example5,6-dichloronaphthol. When the naphthol was a 5,6-dihalonaphthol (RR) itwas reacted with either the appropriately substituted benzaldehyde (BB),alcohol (CC), toluene (DD), or hydrochloride (EE) and a borane-pyridinecomplex under acidic conditions, or a base, for example, sodium hydrideor triethylamine, in a solvent, for example DMF, or a phosphine complex,for example n-butylphosphine, and DPAD in a solvent, for example, THF,to form the targeted 1-substitutedalkylthio oralkoxy-4-((5,6-substituted naphth-1-yl)oxyalkyl)benzene (Ia), forexample,(2-(4-((5,6-dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine.

[0233] A halo substituent, for example chloro, can be added to the4-postion of naphthol ring at this time by reacting the appropriatelysubstituted naphthol (MM) or (RR) with a sulfuryl halide, for example,sulfuryl chloride, in a solvent to yield the appropriately substituted4-halonaphthol (SS). The appropriately substituted 4-halonaphthol (SS)can be reacted either the appropriately substituted benzaldehyde (BB),alcohol (CC), toluene (DD), or hydrochloride (EE) in the mannerdescribed above to form the targeted 1-substitutedalkylthio oralkoxy-4-((5,6-substituted naphth-1-yl)oxyalkyl)benzene (Ib), forexample,(2-(4-((4,6-dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine.

[0234] As depicted in Schema 2, compounds of the present inventionwherein U is nitrogen and n is 1 were prepared by reacting theappropriately substituted benzaldehyde (BB) with the appropriatelysubstituted 1-aminonaphthalene (SM12), for example,1-amino-4-chloronaphthalene, under acidic conditions to form theappropriately substituted 1-aza-1-naphthyl-2-phenylethene (TT), whichwas then reduced with a reducing agent in the manner disclosed above toyield the targeted targeted 1-substituted -4-((substitutednaphth-1-yl)aminoalkyl)benzene (IV), for example,(2-(4-(((4-chloronaphthyl)amino)methyl)phenoxy)-ethyl)diethylamine.

[0235] As depicted in Schema 3, compounds of the present inventionwherein U is —CH₂— and n is 1 were prepared by reacting theappropriately substituted 1-aminonaphthalene (SM12) with theappropriately substituted 4-methylthio-, 4-methoxy-, or4-methylamino-1-vinylbenzene (SM13) with t-butylnitrite, in a solvent,for example, acetonitrile, in the presence of palladium acetate to formthe appropriately substituted 2-(4-methylthio-, 4-methoxy-, or4-methylaminophenyl)vinylnaphthalene (UU). The vinylnaphthalene was thenhydrogenated in a solvent, for example, ethanol, with a palladium oncarbon to form the appropriately substituted 2-(4-methylthio-,4-methoxy-, or 4-methylaminophenyl)ethylnaphthalene (WW). Theethylnaphthalene (WW) was then reacted in solvent, for example methylenechloride, with boron tribromide to form the appropriately substituted2-(4-thio-, 4-hydroxy-, or 4-aminophenyl)ethylnaphthalene (XX). Theethylnaphthalene (XX) was in turn reacted with the appropriatelysubstituted alkyl chloride hydrochloride salt (SM2) and an excess of abase, for example, potassium carbonate, in solvent, for example, DMF, toform the targeted 1-substituted -4-((substitutednaphth-1-yl)ethyl)benzene (V), for example,(2-(4-(((4-chloronaphthyl)amino)methyl)phenoxy)-ethyl)diethylamine.

[0236] Schema 4 depicts another route in which the compounds of thepresent invention may be prepared. In Schema 4, the appropriatelysubstituted benzaldehyde (SM3) is reacted with a haloalkylbromide, forexample, 1-bromo-2-chloromoethane, to yield the appropriatelysubstituted 4-haloalkoxybenzaldehdye (YY), which in turn is reduced witha reducing agent in an alcohol, for example methanol, in the mannerdescribed above to form the appropriately substituted4-haloalkoxyphenylmethan-1-ol (ZZ). The phenylmethan-1-ol (ZZ) was thenreacted at 0° C. to ambient temperature with the appropriatelysubstituted naphthol or phenol (SM14), a phosphine complex, and DPAD ina solvent in the manner described above to yield the correspondinghalo-1-(4-substituted naphthyl- or 4-substitutedphenyl)oxy)methyl)phenoxy)alkane (AAA), for example,2-chloro-1-(4-((4-chloronaphthyloxy)methyl)phenoxy)ethane. The alcane(AAA) was then reacted with the appropriate substituent, for example,cis-2,6-dimethylpiperidine, and a base in acetonitrile to form thecorresponding, 1-(subtituted alkoxy)-4-((4-substituted naphthyl orphenyl)oxy)methyl)benzene (VI), for example1-(2-(2,6-dimethylpiperidyl)ethoxy)-4-((4-chloronaphthyloxy)methyl)benzene.At this point, the benzene (VI) can optionally be reacted with3-chloroperoxybenzoic acid in chloroform at 0° C. to form thecorresponding 2-(4-substituted naphthyl orphenyl)oxy)methyl)phenoxy)alkyl)alkanone (VII), for example,amino(2-(4-((5,6-dichloronaphthyloxy)methyl)phenoxy)ethyl)diethyl-1-oneSchema 5 illustrates yet another route for preparing the compounds ofthe present invention wherein R¹ is a disubstituted amino. In schema 5,the appropriately substituted (4-hydroxyphenyl)methan-1-ol (SM4) wasreacted with a bromomethylisocyanate and a reducing agent, for examplepotassium carbonate, in a solvent, for example, DMF, in the mannerdisclosed above to form the corresponding(4-(cyanomethoxy)phenyl)methan-1-ol (BBB). The methan-1-ol (BBB) wasthen reacted with sulfinyl chloride in a solvent, for example,chloroform, at 0° C. to form the corresponding4-(cyanomethoxy)-1-(chloromethyl)benzene (CCC), which was in turnreacted with the appropriately substituted naphthol or phenol (SM14) anda reducing agent, for example, potassium carbonate, in a solvent, forexample DMF, in the manner described above to yield the corresponding1-(((4-substituted naphthyl- or 4-substitutedphenyl)oxy)methyl)-4-(cyanomethoxy)benzene (DDD). The4-(cyanomethoxy)benzene (DDD) was reacted with borane in a solvent, forexample, THF, at 0° C. to form the appropriately substituted1-(((4-substituted naphthyl- or 4-substitutedphenyl)oxy)methyl)-4-(aminomethoxy)benzene (EEE). The4-(aminomethoxy)benzene (EEE) was in turn reacted with the appropriateoxoalkyl chloride, for example, acetyl chloride, in a solvent, forexample, pyridine or THF, at 0° C. to yield the corresponding1-(((4-substituted naphthyl- or 4-substitutedphenyl)oxy)methyl)-4-(oxoalkylaminomethoxy)benzene (FFF). The4-(oxoalkylaminomethoxy)benzene (FFF) was then reacted with borane in asolvent in the manner described above to yield the targeted1-(((4-substituted naphthyl- or 4-substitutedphenyl)oxy)methyl)-4-(alkylaminomethoxy)benzene (VIII). At this point,additional moieties can be optionally added to the amino group byreacting the 4-(alkylaminomethoxy)benzene (VIII) with the appropriatesubstituted alkyl, alkoxy, or alkoxyalkyl halide and a base, forexample, triethylamine, to yield the target 1-(((4-substituted naphthyl-or 4-substituted phenyl)oxy)methyl)-4-((disubstitutedamino)methoxy)benzene (IX).

[0237] The present invention is now described in more detail byreference to the following examples, but it should be understood thatthe invention is not construed as being limited thereto.

EXAMPLE 1

[0238] This example illustrates one protocol for the preparation of(2-(4-((5,6-dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine(Compound 223).

[0239] Step A (6-aminonapthyl)((4-methylphenyl)sulfonyl)oxy

[0240] A stirred solution of 5.0 grams (0.031 mole) of6-amino-1-naphthol (available from TCI America, Portland, Oreg.) and 6.1grams (0.032 mole) of p-toluenesulfonyl chloride (available from AldrichChemical Company, Milwaukee, Wis.) in 225 mL of methylene chloride(available from J. T. Baker Inc., Phillipsburg, N.J.) was cooled in anice bath, and 5.3 grams (0.038 mole) of triethylamine was addeddropwise. The reaction mixture was then allowed to warm to ambienttemperature where it stirred for about 18 hours. After this time, thereaction mixture was washed with three 75 mL portions of water, driedwith sodium sulfate, and filtered. The filtrate was concentrated underreduced pressure, yielding 9.1 grams of title compound. The NMR spectrumwas consistent with the proposed structure.

[0241] Step B (5,6-dichloronapthyl)((4-methylphenyl)sulfonyl)oxy

[0242] Under a nitrogen atmosphere, 2.0 grams (0.0064 mole) of(6-aminonapthyl)((4-methylphenyl)sulfonyl)oxy was taken up in 6 mL ofacetonitrile (available from EM Sciences, Gibbstown, N.J.). The mixturewas stirred at ambient temperature for ten minutes and then 5.1 grams(0.038 mole) of copper (II) chloride was added. The resulting mixturewas stirred at ambient temperature for ten minutes. At the conclusion ofthis period, the mixture was cooled in an ice bath and 0.85 mL (0.0064mole) of t-butyl nitrite was added dropwise during a ten minute period.Upon completion of addition, the reaction mixture was stirred at 7-8° C.for 1.25 hours. At the conclusion of this period, the reaction mixturewas poured into an ice-cold aqueous 10% hydrochloric acid solution andextracted with ethyl acetate. The extract was washed with one 25 mLportion of an aqueous solution saturated with sodium chloride, driedwith sodium sulfate and filtered. The filtrate was concentrated underreduced pressure, yielding about 2.0 grams of crude product. The crudeproduct was purified by column chromatography on silica gel, yielding1.0 grams of title compound; mp 104-109° C. The NMR spectrum wasconsistent with the proposed structure.

[0243] Step C 5,6-dichloronaphthol

[0244] To a mixture of 0.85 gram (0.0023 mole) of(5,6-dichloronapthyl)((4-methylphenyl)sulfonyl)oxy in 40 mL of ethanol(available from J. T. Baker Inc.) was added 5 mL of tetrahydrofuran(THF, available from Aldrich Chemical Company). The resulting mixturewas stirred to effect dissolution and then a solution of 1.3 grams(0.023 mole) of potassium hydroxide (available from VWR ScientificProducts, Bridgeport, N.J.) in 40 mL of water was added. Upon completionof addition; the reaction mixture was under reflux for one hour. Afterthis time, most of the solvent was removed under reduced pressure toyield a residue. The residue was extracted with one 20 mL portion ofdiethyl ether. The extract was acidified to a pH of 5-6 with ice-coldaqueous 5% hydrochloric acid and then extracted with ethyl acetate. Theethyl acetate extract was washed with an aqueous solution saturated withsodium chloride, dried with sodium sulfate and filtered. The filtratewas concentrated under reduced pressure, yielding 0.33 gram of titlecompound. The NMR spectrum was consistent with the proposed structure.

[0245] Step D (4-(2-diethylamino)ethoxy)phenyl)methan-1-ol

[0246] A solution of 37.2 grams (0.22 mole) of 2-(diethylamino)ethylchloride hydrochloride (available from Aldrich Chemical Company), 26.8grams (0.22 mole) of 4-hydroxybenzyl alcohol (available from AldrichChemical Company) and 89 grams (0.65 moles) of potassium carbonate(available from VWR Scientific Products) in 1200 mL ofN,N-dimethylformamide (DMF, available from EM Sciences) was stirred atambient temperature for about 18 hours. After this time, the solvent wasremove under reduced pressure, yielding a residue. The residue was takenup in water and then extracted with ethyl acetate. The extract waswashed with one portion of an aqueous 10% sodium hydroxide solutionfollowed by one portion of water and then one portion of an aqueoussolution saturated with sodium chloride, dried with sodium sulfate andfiltered. The filtrate was concentrated under reduced pressure, yielding2.38 grams of title compound. The NMR spectrum was consistent with theproposed structure.

[0247] Step E Compound 223

[0248] A stirred solution of 0.33 gram gram (0.0016 mole) of5,6-dichloronapthol and 0.35 gram (0.0016 mole) of(4-(2-diethylamino)ethoxy)phenyl)methan-1-ol in 15 mL of THF was cooledin an ice bath, and 0.24 mL (0.0017 mole) of tributylphosphine(available from Aldrich Chemical Company) followed by 0.42 gram (0.0017mole) of 1-1′-(azadicarbomyl)dipiperidine (available from AldrichChemical Company) were added. Upon completion of addition, the reactionmixture was allowed to warm to ambient temperature where it stirred for72 hours. After this time, the reaction mixture was diluted with ethylacetate, and an aqueous solution saturated with sodium chloride wasadded. The organic layer was separated, dried with magnesium sulfate,and filtered. The filtrate was concentrated under reduced pressure,yielding about 0.45 gram of crude product. The crude product waspurified by column chromatography on silica gel, yielding 0.13 gram ofCompound 223. The NMR spectrum was consistent with the proposedstructure.

EXAMPLE 2

[0249] This example illustrates one protocol for the preparation of thehydrochloride salt of(2-(4-((5,6-dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine(Compound 224).

[0250] Compound 225 (prepared in the manner of Example 1), 0.07 gram(0.00017 mole), was taken up in 1 mL of methylene chloride (availablefrom EM Sciences) and 1 mL of one molar hydrochloric acid in diethylether (available from Aldrich Chemical Company) was added. The solventwas removed under reduced pressure to yield a solid. The solid was takenup in heptane. The resulting precipitate was collected by vacuumfiltration, yielding 0.07 gram of Compound 226; mp 204-206° C. The NMRspectrum was consistent with the proposed structure.

EXAMPLE 3

[0251] This example illustrates one protocol for the preparation of(2-(4-((6-quinolylamino)methyl)phenoxy)ethyl)diethylamine (Compound 15).

[0252] Step A 4-(2-(diethylamino)ethoxy)benzaldehyde

[0253] A solution of 5.0 grams (0.041 mole) of 4-hydroxybenzaldehdye(available from Aldrich Chemical Company), 8.5 grams (0.049 mole) of2-diethylaminoethyl chloride hydrochloride (available from AldrichChemical Company), and 13.5 grams (0.098 mole) of potassium carbonate(available from J. T. Baker Inc.) in 100 mL of DMF was stirred atambient temperature for 72 hours. At the conclusion of this period, thereaction mixture was poured into 100 mL of water and extracted withthree 50 mL portions of diethyl ether. The combined extracts were washedwith one 25 mL portion of water, dried with sodium sulfate, andfiltered. The filtrate was concentrated under reduced pressure, yielding5.1 grams of title compound. The NMR spectrum was consistent with theproposed structure.

[0254] Step B Compound 15

[0255] To a stirred solution of 1.0 gram (0.0045 mole) of4-(2-(diethylamino)ethoxy)benzaldehyde and 0.65 gram (0.0045 mole) of6-aminoquinoline (available from Aldrich Chemical Company) in 25 mL of1,2-dichloroethane (DCE, available from Aldrich Chemical Company)wasadded 0.3 mL (0.0045 mole) of glacial acetic acid (available from J. T.Baker Inc.) followed by 1.4 grams (0.0068 mole) of sodiumtriacetoxyborohydride (available from Aldrich Chemical Company). Uponcompletion of addition, the reaction mixture was stirred at ambienttemperature for three hours. At the conclusion of this period, 50 mL of10% aqueous sodium hydroxide was added dropwise. The resulting solutionwas extracted with three 25 mL portions of diethyl ether. The extractswere combined, washed with one 25 mL portion of an aqueous solutionsaturated with sodium chloride, dried with sodium sulfate and filtered.The filtrate was concentrated under reduced pressure, yielding 1.25grams of a dark brown paste. The dark brown paste was purified by columnchromatography on silica gel, yielding 0.13 gram of Compound 15. The NMRspectrum was consistent with the proposed structure.

EXAMPLE 4

[0256] This example illustrates one protocol for the preparation of(2-(4-(((4-chloronaphthyl)amino)methyl)-2-methoxyphenoxy)ethyl)diethylamine(Compound 263).

[0257] Step A 4-(2-(diethylamino)ethoxy)-2-methoxybenzaldehyde

[0258] This compound was prepared in the manner of Step A, Example 3,using 2.5 grams (0.016 mole) of 4-hydroxy-2-methoxybenzaldehdye(available from Lancaster Synthesis Inc., Windham, N.H.), 3.4 grams(0.02 mole) of 2-diethylaminoethyl chloride hydrochloride, and 5.5 grams(0.04 mole) of potassium carbonate in 75 ML of DME. The yield of thetitle compound was 2.6 grams. The NMR spectrum was consistent with theproposed structure.

[0259] Step B Compound 263

[0260] This compound was prepared in the manner of Step B, Example 3,using 1.0 gram (0.004 mole) of4-(2-(diethylamino)ethoxy)-2-methoxybenzaldehyde, 0.71 gram (0.004 mole)of 1-amino-4-chloronaphthalene (available from Aldrich ChemicalCompany), 0.25 mL (0.004 mole) of glacial acetic acid, 1.3 grams (0.006mole) of sodium triacetoxyborohydride and 50 mL of 1,2-dichloroethane(DCE). The yield of Compound 263 was 0.52 gram. The NMR spectrum wasconsistent with the proposed structure.

EXAMPLE 5

[0261] This example illustrates one protocol for the preparation of(2-(4-(((4-chloronaphthyl)methoxy)methyl)phenoxy)ethyl)diethylamine(Compound 8).

[0262] Step A (4-(2-diethylamino)ethoxy)phenyl)metian-1-ol

[0263] A solution of 4.0 grams (0.08 mole) of4-(2-(diethylamino)ethoxy)benzaldehyde (prepared in the manner of StepA, Example 3) and 2.7 grams (0.08 mole) of sodium borohydride (availablefrom Aldrich Chemical Company) in 40 mL of methanol (available from J.T. Baker Inc,) was stirred at ambient temperature for about 18 hours.After this time, the reaction mixture was quenched with water andextracted with several portions of methylene chloride. The organicextracts were combined, dried with magnesium sulfate, and filtered. Thefiltrate was concentrated under reduced pressure, yielding 4.1 grams oftitle compound.

[0264] Step B 4-chloronaphthalenecarbaldehye

[0265] To a stirred solution of 6.7 grams (0.026 mole) of a 1.0 Msolution of tin(iv) chloride in dichloromethane (available from AldrichChemical Company) in 10 mL of methylene chloride was added 3.0 grams(0.026 mole) of ℑ,ℑ-dichloromethyl methyl ether (available from AldrichChemical Company). The resulting solution was stirred for one hour atambient temperature. After this time, a solution of 2.8 mL (0.021 mole)of 4-chloronaphthalene was added. Upon completion of addition, thereaction mixture was stirred at ambient temperature for about 18 hours.At the conclusion of this period, the reaction mixture was quenched withwater, washed with water followed by an aqueous solution saturated withsodium chloride, dried with sodium sulfate and filtered. The filtratewas concentrated under reduced pressure, yielding about 2.1 grams oftitle compound.

[0266] Step C (4-chloronaphthyl)methan-1-ol

[0267] This compound was prepared in the manner of Step C, Example 1,using 2.1 grams (0.01 1 mole) of 4-chloronaphthalenecarbaldehye, 70 mLof methanol, 20 mL of THF, and 2 grams (0.054 mole) of sodiumborohydride. This preparation differs in that sodium borohydride wasused rather than a solution of potassium hydroxide in water. The yieldof the title compouid was 1.9 grams.

[0268] Step D Compound 8

[0269] This compound was prepared in the manner of Step E, Example 1,using 0.5 gram (0.0026 mole) of (4-chloronaphthyl)methan-1-ol, 0.6 gramof (4-(2-diethylamino)ethoxy)phenyl)methan-1-ol, 70 mL of THF, 0.79 mL(0.0031 mole) of tributylphosphine, and 0.73 gram (0.0029 mole) of1-1′-(azadicarbomyl)dipiperidine. The yield of Compound 8 was 0.3 gram.

EXAMPLE 6

[0270] This example illustrates one protocol for the preparation of1-(2-(2,6-dimethylpiperidyl)ethoxy)-4-((4-chloronaphthyloxy)methyl)benzene(Compound 106).

[0271] Step A Mixture of 4-(2-bromoethoxy)benzaldehyde and4-(2-chloroethoxy)benzaldehyde

[0272] Sodium hydride (60% dispersion in mineral oil, available fromAldrich Chemical Company),4.4 grams (0.11 mole), was washed with threeportion of hexane (available from J. T. Baker Inc.) and 200 mL of DMFwas added. The resulting mixture was cooled to 0 C and 50 mL (0.6 mole)of 1-bromo-2-chloromoethane (available from Aldrich Chemical Company)followed by 12.2 grams (0.1 mole) 4-hydroxybenzaldehyde were added. Uponcompletion of addition, the reaction mixture was heated to 40° C. whereit stirred for about 72 hours. After this time, the reaction mixture wasextracted with several portions of ethyl acetate. The organic extractswere combined, dried with magnesium sulfate, and filtered. The filtratewas concentrated under reduced pressure, yielding 7.4 grams of titlemixture. The NMR spectrum was consistent with the proposed structure.This compound was prepared several times in the manner described above.

[0273] Step B Mixture of (4-(2-bromoethoxy)phenyl)methan-1-ol and(4-(2-chloroethoxy)phenyl)methan-1-ol

[0274] This compound was prepared in the manner of Step C, Example 1,using 8.7 grams (0.047 mole) of the mixture of4-(2-bromoethoxy)benzaldehyde and (4-(2-chloroethoxy)phenyl)methan-1-ol,400 mL of methanol, and 3.5 grams (0.094 mole) of sodium borohydride.This preparation differs in that no THF was used and sodium borohydridewas used rather than a solution of potassium carbonate in water. Theyield of the title mixture was 8.4 grams. The NMR spectrum wasconsistent with the proposed structure.

[0275] Step C. 2-chloro-1-(4-((4-chloronaphthyloxy)methyl)phenoxy)ethane

[0276] A stirred solution of 8.4 grams (0.045 mole) of the mixture of(4-(2-bromoethoxy)phenyl)methan-1-ol and(4-(2-chloroethoxy)phenyl)methan-1-ol, 8.1 grams (0.045 mole) of4-chloronaphthol, and 13.7 mL (0.054 mole) of tributylphosphine in 500mL of THF was cooled in an ice bath and 12.6 grams (0.049 mole) of1-1′-(azodicarbomyl)dipiperidine was added. Upon completion of addition,the reaction mixture was allowed to warm to ambient temperature where itstirred for 24 hours. After this time, the solvent was reduced underreduce pressure, yielding a solid. The solid was purified by columnchromatography on silica gel, yielding 15 grams of crude product. Thecrude product was further purified by column chromatography on silcagel, yielding 6.7 grams of title compound.

[0277] Step D Compound 106

[0278] A stirred mixture of 0.4 grams (0.001 mole) of2-chloro-1-(4-((4-chloronaphthyloxy)methyl)phenoxy)ethane and 5 mL(0.037 mole) of cis-2,6-dimethylpiperidine was heated to just belowreflux for about 72 hours. After this time, the reaction mixture wasanalyzed by thin layer chromatography (TLC), which indicated thereaction was incomplete. The reaction mixture was concentrated underreduced pressure and subject to column chromatography on silica gel,yielding 0.2 gram of compound 106. The NMR spectrum was consistent withthe proposed structure.

EXAMPLE 7

[0279] This example illustrates one protocol for the preparation ofamino(2-(4-((5,6-dichloronaphthyloxy)methyl)phenoxy)ethyl)diethyl-1-one(Compound 183).

[0280] (2-(4-((5,6-Dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine(prepared in the manner of Example 1), 0.1 gram (0.0003 mole), was takenup in 10 mL of chloroform (available from EM Sciences). The resultingsolution was cooled to 0° C. in an ice bath and 0.09 gram (0.0004 mole)of 3-chloroperoxybenzoic acid (available from Aldrich Chemical Company)was added. Upon completion of addition, the resulting mixture wasstirred for ten minutes and then the ice bath was removed. The reactionmixture was allowed to warm to ambient temperature where it stirred for35 minutes. At the conclusion of this period, the reaction mixture waspoured into a solution of 25 mL of chloroform and 10 mL of aqueous 5%sodium hydroxide. The organic layer was separated, dried with sodiumsulfate and filtered. The filtrate was concentrated under reducedpressure, yielding 0.15 gram of compound 183; mp 81-87° C. The NMRspectrum was consistent with the proposed structure.

EXAMPLE 8

[0281] This example illustrates one protocol for the preparation of(2-(4-((4,6-dichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine(Compound 216).

[0282] Step A 4,6-dichloronaphthol

[0283] This compound was prepared in the manner of Step B, Example 1,using 5.0 grams (0.029 mole) of 6-aminonaphthol, 200 mL of acetonitrile,4 grams (0.03 mole) of copper (II) chloride, and 3.3 grams (0.032 mole)of t-butyl nitrite. The yield of the title compound was 1.4 grams.

[0284] Step B Compound 216

[0285] This compound was prepared in the manner of Step E, Example 1,using 0.4 gram (0.0022 mole) of 4,6-dichloronaphthol, 0.49 gram (0.0022mole) of (4-(2-diethylamino)ethoxy)phenyl)methan-1-ol, 80 mL of THF, 0.5gram (0.0025 mole) of tributylphosphine, and 0.55 gram (0.0022 mole) of1-1′-(azodicarbomyl)dipiperidine. The yield of Compound 216 was 0.3gram.

EXAMPLE 9

[0286] This example illustrates one protocol for the preparation of(2-(4-(((4-chloronaphthyl)amino)methyl)phenoxy)ethyl)diethylamine(Compound 84).

[0287] A stirred solution of 0.2 gram (0.0001 mole) of4-(2-(diethylamino)ethoxy)benzaldehyde (prepared in the manner of StepA, Example 3), 0.22 gram (0.0001 mole) of 1-amino-4-chloronaphthalene(available from Aldrich Chemical Company), and one drop ofp-toluenesulfonic acid monohydrate (available from Aldrich ChemicalCompany) in 5 mL of toluene was heated at reflux for ten hours. At theconclusion of this period, the reaction mixture was concentrated underreduced pressure, yielding a residue. The residue was taken up in 5 mLof methanol and about 0.2 grams (0.004 mole) of sodium borohydride wasadded. The resulting mixture was stirred at ambient temperature forabout 18 hours. After this time, the mixture was quenched with water andextracted with several portions of diethyl ether. The extracts werecombined, dried with sodium sulfate and filtered. The filtrate wasconcentrated under reduced pressure, yielding 0.8 gram of Compound 84.The NMR spectrum was consistent with the proposed structure.

EXAMPLE 10

[0288] This example illustrates one protocol for the preparation of(2-(4-(((4-chloronaphthyl)amino)methyl)phenylthio)ethyl)diethylamine(Compound 71).

[0289] Step A (4-(2-diethylamino)ethylthio)phenyl)methan-1-ol

[0290] Under a nitrogen atmosphere, 0.6 gram (0.017 mole) of lithiumaluminum hydride (available from Aldrich Chemical Company) wastaken upin 20 mL of THF. The resulting mixture was stirred to effect dissolutionand a solution of one gram (0.007 mole) of 2-mercaptobenzoic acid(available from Aldrich Chemical Company) 10 mL of THF was added. Theresulting was stirred for 70 minutes. At the conclusion of this period,the solution was cooled in an ice bath and 10 mL of ethyl acetate wascarefully added during a 30 minute period. Upon completion of addition,5 mL of water followed by 1.3 grams (0.008 mole) of2-(diethylamino)ethyl chloride hydrochloride was added. Upon completionof addition, the reaction mixture was allowed to warm to ambienttemperature where it stirred for about 18 hours. After this time, about10 mL of aqueous 10% sodium hydroxide followed by an addition 10 mL ofethyl acetate was added. The resulting mixture was filtered. The organiclayer of the filtrate was separated from the aqueous layer, washed withan aqueous solution saturated with sodium chloride, dried with sodiumsulfate and filtered, yielding 3.32 grams of a yellow liquid. The yellowliquid was purified by column chromatography on silica gel, yielding 0.5gram of title compound. The NMR spectrum was consistent with theproposed structure.

[0291] Step B 4-(2-(diethylamino)ethylthio)benzaldehyde

[0292] Under a nitrogen atmosphere, a stirred solution of 0.2 mL (0.003mole) of dimethyl sulfoxide (DMSO, available from Aldrich ChemicalCompany) in 10 mL of methylene chloride of was cooled to −60° C. and 0.2mL (0.002 mole) of oxalyl chloride (available from Aldrich ChemicalCompany) was added. The resulting solution was stirred at −60° C. for 15minutes. At the conclusion of this period, a solution of 0.5 gram (0.002mole) of (4-(2-diethylamino)ethylthio)phenyl)methan-1-ol in about 20 mLof methylene chloride was added. The mixture was stirred at −60° C. to−40° C. of 30 minutes and 1.5 mL (0.011 mole) of triethylamine wasadded. Upon completion of addition, the reaction mixture was stirred at−40° C. for 1.5 hours. At the conclusion of this period, the reactionmixture was filtered through a silica gel plug. The filter cake waswashed with one 150 mL portion of ethyl acetate. The filtrate wasconcentrated under reduced pressure, yielding 0.2 gram of titlecompound. The NMR spectrum was consistent with the proposed structure.

[0293] Step C Mixture of(2-(4-(2-aza-2-(4-chloronaphthyl)vinyl)phenylthio)ethyl)-diethylamineand Compound 71

[0294] A solution of 0.2 (0.001 mole) of4-(2-(diethylamino)ethylthio)benzaldehyde, 0.2 gram6-amino-4-chloronaphthalene, 0.4 gram (0.002 mole) of sodiumtriacetoxyborohydride and 10 drops of glacial acetic acid in 10 mL ofDCE was stirred at ambient temperature for about 18 hours. At theconclusion of this period, 50 mL of 10% aqueous sodium hydroxidefollowed by 75 mL of ethyl acetate was added. The organic layer wasseparated from the aqueous layer and filtered through phase separatedfilter paper, yielding 0.4 gram of crude product. This crude product wascombined with 0.1 gram of crude product prepared in a similar experimentto yield a total of 0.5 gram of crude product. The 0.5 gram of crudeproduct was purified by column chromatography on silica gel, yielding0.1 gram of mixture of(2-(4-(2-aza-2-(4-chloronaphthyl)vinyl)phenylthio)ethyl)diethylamine andCompound 71. The NMR spectrum was consistent with the proposedstructure.

[0295] Step D Compound 71

[0296] A stirred solution of 0.1 gram (0.0008 mole) ofborane-dimethylamine complex (available from Aldrich Chemical Company)and 0.1 gram (0.0003 mole) of the mixture of(2-(4-(2-aza-2-(4-chloronaphthyl)vinyl)phenylthio)ethyl)diethylamine andCompound 71 in 2 mL of glacial acetic acid was heated at 60° C. forthree hours. After this time, the reaction mixture was allowed to coolto ambient temperature and 5 ml of ethyl acetate was added. Theresulting mixture was washed with an aqueous 10% sodium hydroxidesolution. The organic layer was separated from the aqueous layer andfiltered through phase separation filter paper, yielding 0.1 gram of anoil. The oil was purified by column chromatography on silica gel,yielding 0.1 gram of product. The 0.1 gram of product was combined with0.1 gram of product from a previous experiment to yield 0.2 gram ofCompound 71. The NMR spectrum was consistent with the proposedstructure.

EXAMPLE 11

[0297] This example illustrates one protocol for the preparation ofdiethyl(2-(4-((2,3,4-trichlorophenoxy)methyl)phenoxy)ethyl)amine(Compound 308).

[0298] Step A (2-(4-chloromethyl)phenoxy)ethyl)diethylaminehydrochloride

[0299] Under a nitrogen atmosphere, 2 mL (0.027 mole) of thionylchloride (available from J. T. Baker Inc.) was added dropwise to astirred solution of 5.8 grams (0.026 mole) of4-(2-(diethylamino)ethoxy)benzaldehyde prepared in the manner of Step A,Example 3) in 150 mL of methylene chloride. Upon completion of addition,the reaction mixture was stirred at ambient temperature for about 2.5hours. After this time, the reaction mixture was heated to 50° C. andthe solvent was removed under reduced pressure, yielding 7.2 grams oftitle compound. The NMR spectrum was consistent with the proposedstructure.

[0300] Step B Compound 308

[0301] A stirred solution of 0.3 gram (0.001 mole) of(2-(4-chloromethyl)phenoxy)ethyl)diethylamine hydrochloride, 0.2 gram(0.0009 mole) of 2,3,4-trichlorophenol (available from Aldrich ChemicalCompany), 0.9 gram (0.003 mole) of cesium carbonate (available fromAldrich Chemical Company) and a catalytic amount of sodium iodide(available from Aldrich Chemical Company) in 10 mL of acetone (availablefrom J. T. Baker Inc.) was heated to 60 C for about 18 hours. After thistime, the solvent was removed under reduced pressure and about 10 mL ofmethylene chloride was added. The resulting solution was filtered, andthe filtrate was filtered through a silica gel pad, yielding 0.2 gram ofCompound 308. The NMR spectrum was consistent with the proposedstructure.

EXAMPLE 12

[0302] This example illustrates one protocol for the preparation ofdiethyl(2-(4-((2,5-difluorophenoxy)methyl)phenoxy)ethyl)amine (Compound346).

[0303] This compound was prepared in the manner of Step B, Example 11,using 0.3 gram (0.001 mole) of(2-(4-chloromethyl)phenoxy)ethyl)diethylamine hydrochloride, 0.1 gram(0.0009 mole) of 2,5-difluorophenol (available from Aldrich ChemicalCompany), 0.9 gram (0.003 mole) of cesium carbonate and a catalyticamount of sodium iodide in 10 mL of acetone. The yield of Compound 346was 0.2 gram. The NMR spectrum was consistent with the proposedstructure.

EXAMPLE 13

[0304] This example illustrates one protocol for the preparation of1,2-dichloro-5-{[4-(4-ethylpiperazinyl)phenyl]methoxy}naphthalene(Compound 355).

[0305] Step A 4-piperazinylbenzonitrile

[0306] Under a nitrogen atmosphere, a stiffed miture of 10.0 grams(0.055 mole) of 4-bromobenzonitrile (available from Aldritch ChemicalCompany) and 23.7 grams (0.28 mole) of piperazine (available fromAldrithc Chemical Company was heated at 120° C. for about 45 hours.After this time, the reaction mixture was taken up in 150 ml of aqueous10% sodium hydroxide. The resulting solution was extracted with three 50mL portions of methylene chloride. The combined extracts were washedwith one 50 mL portion of an aqueous saturated sodium chloride solution,dried with sodium sulfate, and filtered. The filtrate was concentratedunder reduced pressure, yielding 8.6 grams of a green paste. The greenpaste was purified by column chromatography on silica gel, yielding 3.8grams of a paste. The paste was taken up in 50 mL of diethyl ether. Theresulting solution was warned on a rotovap and decanted away from theinsoluble paste. The decantate was concentrated, yielding 3.2 grams ofthe title comound. The NMR spectrum was consistent with the proposedstructure.

[0307] Step B 4-(4-ethyl)piperazinylbenzonitrile

[0308] Under a nitrogen atmosphere, a stirred solution of 3.16 grams(0.017 mole) of 4-piperazinylbenzonitrile, 2.0 mL (0.025 mole) ofiodoethane (available from Aldritch Chemical Company), and 7.1 mL (0.051mole) of triethylamine in 50 mL of TBF was heated at reflux for aboutthree hours. At the conclusion of this period, the reaction mixture wasallowed to cool to ambient temperature and 100 mL of water was added.The resulting solution was extracted with two 50 mL portions of diethylether. The combined extracts were washed with 100 mL portion of water,dried with sodium sulfate, and filtered. The filtrate was concentratedunder reduced pressure, yielding 3,2 grams of crude product. The crudeproduct was purified by column chromatography on silica gel, yielding2.9 grams of tilte compound. The NMR spectrum was consistent with theproposed structure.

[0309] Step C [4-(4-ethylpiperazinyl)benzaldehyde

[0310] Under a nitrogen atmosphere, a stirred solution of 2.8 grams(0.013 mole) of 4-(4-ethyl)piperazinylbenzonitrile in 35 mL of anhydroustoluene (available from Aldrich Chemical Company) was cooled to −70° C.and 12 mL (0.02 mole) of diisobutylaluminum hydride (1.5M in toluene,available from Aldritch Chemical Company) was added dropwise at a rateto maintain the temperature below −60° C. during about a 15 minuteperiod. Upon completion of addition, the reaction mixture was stirred at−60° C. for two hours. At the conclusion of this period, 10 mL ofmethanol was added dropwise followed by 10 mL of water. The resultingsolution was allowed to warm to ambient temperature. Once at theprescribed temperature, 10 mL of methylene chloride was added. Theresulting mixture was filtered and the filtrate was transferred to aseparatory fimnel. The organic layer was separated from the aqueouslayer, dried with sodium sulfate, and filtered. The filtrate wasconcentrated under reduced pressure, yielding 1.6 grams of an orangepaste. The orange pasted was was filtered through a silica gel plug. Thefilter cake was washed with one 75 mL portion of methylene chloridefollowed by one 50 mL portion of a 5% methanol/95% methylene chloridesolution. The filtrate was concentrated under reduced pressure, yielding0.5 gram of title compound. The NMR spectrum was consistent with theproposed structure.

[0311] Step D [4-(4-ethylpiperazinyl)phenyl]methan-1-ol

[0312] This compound was prepared in the manner of Step A, Example 5,using 0.4 gram (0.019 mole) of [4-(4-ethylpiperazinyl)benzaldehyde and0.4 gram (0.01 mole) of sodium borohydride in 40 mL of absolute ethanol(available from J. T. Baker Inc.) The yield of the title compound was0.3 gram. The NMR Spectrum was consistend with the proposed structure.

[0313] Step E Compound 355

[0314] This compound was prepared in the manner of Step E, Example 1,using 0.23 gram gram (0.0011 mole) of 5,6-dichloronapthol, 0.25 gram(0.0011 mole) of [4-(4-ethylpiperazinyl)phenyl]methan-1-ol, 0.36 mL(0.0014 mole) of tributylphosphine, and 0.35 gram (0.0014 mole) of1-1′-(azadicarbomyl)dipiperidine in 15 mL of THF. The yield of compound355 was 0.04 gram. The NMR spectrum was consistent with the proposedstructure.

EXAMPLE 14

[0315] This example illustrates one protocol for the preparation of5-{[4-(8-aza-1,4-dioxaspiro[4.5]dec-8-yl)phenyl]methoxy}-1,2-dichloronaphthalene(Compound 362).

[0316] Step A 5-[(4-bromophenyl)methoxy]-1,2-dichloronaphthalene

[0317] A stirred mixture of 4.0 grams (0.019 mole) of5,6-dichloronapthol in 60 mL of THF was cooled in an ice bath and 1.1grams (0.023 mole) of Sodium hydride (60% dispersion in mineral oil) wasadded during a ten minute period. Upon completion of addition, themixture was stirred for twenty minutes. After this time, a solution of5.8 grams (0.023 mole) of 4-bromobenzyl bromide (available from AldrichChemical Company) in 40 mL of THF was added dropwise. Upon completion ofaddition, the reaction mixture was allowed towarm to ambient temperaturewhere it stirred for seven days. After this time, the reaction mixturewas taken up in 100 ml of water. The resulting solution was extractedwith two 200 mL portions of diethyl ether. The combined extracts werewashed with one 75 mL portion of a 10% aqueous lithium chloridesolution, dried with sodium sulfate, and filtered. The filtrate wasconcentrated under reduced pressure, yielding the crude product. Thecrude product was triturated with a mixture of diethyl ether andpetroleum ether. The resulting solid was collected by filtration,yielding 5.3 grams of the title comound. The NMR spectrum was consistentwith the proposed structure.

[0318] Step B Compound 362

[0319] To a 100 mL roundbottom flask was added 0.02 gram (0.00002 mole)of tris(dibenzylideneacetone)dipalladium (o) (available from StremChemical, Newburyport, Mass.), 0.04 gram (0.00006 mole) of racemic2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (available from StremChemical), and 35 mL of toluene. The resulting mixture was evacuated andthen backfilled with nitrogen. This evacuation and backfill procedurewas repeated two more times. The resulting mixture was strtred atambient temperature for 30 minutes. After this time, 0.75 gram (0.002mole) of 5-[(4-bromophenyl)methoxy]-1,2-dichloronaphthalene, 0.52 gram(0.004 mole) of 4-piperidone ethylene ketal (available from LancasterSynthesis Inc.), and 0.38 gram (0.004 mole) of sodium t-butoxide(available from Aldrich Chemical Company) were added to the 100 mL roundbottom flask. Upon completion of addition, the above set forthevacuation and backfill procedure was repeated three times. The reactionmixture was heated to 80-85° C. were it stirred for 4 to 4.5 hours.After this time, the heating was discontinued and the reaction mixturewas stirred for about 18 hours. After this time, the reaction mixturewas filtered through a celite pad and rinsed with toluene. The filtratewas concentrated under reduced pressure yielding the crude product. Thecrude product was purified by column chromatography on neutral alumina(deactivated with 6% water), yielding 0.7 gram of title compound. TheNMR spectrum was consistent with the proposed structure.

[0320] It is well known to one of ordinary skill in the art that thecompounds of formula I of the present invention can containoptically-active and racemic forms. It is also well known in the artthat the compounds of formula I may contain stereoisomeric forms and/orexhibit polymorphism. It is to be understood that the present inventionencompasses any racemic, optically-active, polymorphic or stereoisomericform, or mixtures thereof. It should be noted that it is well known inthe art how to prepare optically-active forms, for example by resolutionof a racemic mixture or by synthesis from optically-active startingmaterials.

[0321] Representative compounds prepared by the methods exemplifiedabove are listed in Table 1. Characterizig properties are given in Table2.

Biological Data

[0322] Candidate insecticides are evaluated for activity against thetobacco budworm (Heliothis virescens [Fabricius]) in a surface-treateddiet test.

[0323] In this test one mL of molten (65-70° C.) wheat germ-basedartificial diet is pipetted into each well of a four by six (24 well)multi-well plate (ID#430345-15.5 mm dia.×17.6 mm deep; Corning CostarCorp., One Alewife Center, Cambridge, Mass. 02140). The diet is allowedto cool to ambient temperature before treatment with candidateinsecticide.

[0324] For a determination of insecticidal activity, solutions of thecandidate insecticides are prepared for testing using a Packard 204DTMultiprobe® Robotic System (Packard Instrument Company, 800 ResearchParkway, Meriden, Conn. 06450), in which the robot first dilutes astandard 50 millimolar DMSO solution of candidate insecticide with a 1:1water/acetone solution (V/V) in a ratio of 1:7 stock solution towater/acetone. The robot subsequently pipettes 40 microliters of theso-prepared solution onto the surface of the diet in each of three wellsin the 24 multi-well plate. The process is repeated with solutions ofseven other candidate insecticides. Once treated, the contents of themulti-well plate are allowed to dry, leaving 0.25 millimoles ofcandidate insecticide on the surface of the diet, or a concentration of0.25 millimolar. Appropriate untreated controls containing only DMSO onthe diet surface are also included in this test.

[0325] For evaluations of the insecticidal activity of a candidateinsecticide at varying rates of application, the test is established asdescribed above using sub-multiples of the standard 50 millimolar DMSOsolution of candidate insecticide. For example, the standard 50millimolar solution is diluted by the robot with DMSO to give 5, 0.5,0.05, 0.005, 0.0005 millimolar, or more dilute solutions of thecandidate insecticide. In these evaluations there are six replicates ofeach rate of application placed on the surface of the diet in the 24multi-well plate, for a total of four rates of application of candidateinsecticide in each plate.

[0326] In each well of the test plate is placed one second instartobacco budworm larvea, each weighing approximately five milligrams.After the larvae are placed in each well, the plate is sealed with clearpolyfilm adhesive tape. The tape over each well is perforated to ensurean adequate air supply. The plates are then held in a growth chamber at25° C. and 60% relative humidity for five days (light 14 hours/day).

[0327] After the five-day exposure period insecticidal activity for eachrate of application of candidate insecticide is assessed as percentinhibition of insect weight relative to the weight of insects fromuntreated controls, and percent mortality when compared to the totalnumber of insects infested.

[0328] The compounds of the present invention were active in the diettest against the tobacco budworm. Over fifteen of the compounds listedin Table 1 exhibited precent growth inhibition values of 70% or greater.Compounds 224, 353, 354,355, 357, 364, 366,367, 368369, 372, and 373-379exhibited percent growth inhibition values of 80% or greater. Table 3gives the insecticidal activity data for compounds tested in the diettest.

[0329] For insecticidal application, the active compounds are formulatedinto insecticidal compositions by admixture in insecticidally effectiveamount with adjuvants and carriers normally employed in the art forfacilitating the dispersion of active ingredients for the particularutility desired, recognizing the fact that the formulation and mode ofapplication of a toxicant may affect the activity of the material in agiven application. Thus, for agricultural use the present insecticidalcompounds may be formulated as granules of relatively large particlesize, as water-soluble or water-dispersible granules, as powdery dusts,as wettable powders, as emulsifiable concentrates, as solutions, or asany of several other known types of formulations, depending on thedesired mode of application.

[0330] These insecticidal compositions may be applied either aswater-diluted sprays, or dusts, or granules to the areas in which insectcontrol is desired. These formulations may contain as little as 0.1%,0.2% or 0.5% to as much as 95% or more by weight of active ingredient.

[0331] Dusts are free flowing admixtures of the active ingredients withfinely divided solids such as talc, natural clays, kieselguhr, flourssuch as walnut shell and cottonseed flours, and other organic andinorganic solids which act as dispersants and carriers for the toxicant;these finely divided solids have an average particle size of less thanabout 50 microns. A typical dust formulation useful herein is onecontaining 1.0 part or less of the insecticidal compound and 99.0 partsof talc.

[0332] Wettable powders are in the form of finely divided particleswhich disperse readily in water or other dispersant. The wettable powderis ultimately applied to the locus where insect control is desiredeither as a dry dust or as an emulsion in water or other liquid. Typicalcarriers for wettable powders include Fuller's earth, kaolin clays,silicas, and other highly absorbent, readily wet, inorganic diluents.Wettable powders normally are prepared to contain about 5-80% of activeingredient, depending on the absorbency of the carrier, and usually alsocontain a small amount of a wetting, dispersing, or emulsifying agent tofacilitate dispersion. For example, a useful wettable powder formulationcontains 80.8 parts of the insecticidal compound, 17.9 parts of Palmettoclay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonatedaliphatic polyester as wetting agents. By way of illustration, compound223 was formulated as a 25% wettable powder (25% WP) as follows:COMPONENT AMOUNT (wt/wt %) Compound 223 (91% pure) 27.5% Diluent 5.0%Wetting Agent 1.0% Dispersing Agent 16.0% UV Stabilizer 0.5%Carrier/Diluent 50.0%

[0333] Other useful formulations for insecticidal applications areemulsifiable concentrates (ECs) which are homogeneous liquidcompositions dispersible in water or other dispersant, and may consistentirely of the insecticidal compound and a liquid or solid emulsifyingagent, or may also contain a liquid carrier, such as xylene, heavyaromatic naphthas, isophorone, or other non-volatile organic solvent.For insecticidal application these concentrates are dispersed in wateror other liquid carrier, and normally applied as a spray to the area tobe treated. The percentage by weight of the essential active ingredientmay vary according to the manner in which the composition is to beapplied, but in general comprises 0.5 to 95% of active ingredient byweight of the insecticidal composition.

[0334] Flowable formulations are similar to ECs except that the activeingredient is suspended in a liquid carrier, generally water. Flowables,like ECs, may include a small amount of a surfactant, and contain activeingredient in the range of 0.5 to 95%, frequently from 10 to 50%, byweight of the composition. For application, flowables may be diluted inwater or other liquid vehicle, and are normally applied as a spray tothe area to be treated. Typical wetting, dispersing, or emulsifyingagents used in agricultural formulations include, but are not limitedto, the alkyl and alkylaryl sulfonates and sulfates and their sodiumsalts; alkylaryl polyether alcohols; sulfated higher alcohols;polyethylene oxides; sulfonated animal and vegetable oils; sulfonatedpetroleum oils; fatty acid esters of polyhydric alcohols and theethylene oxide addition products of such esters; and the additionproduct of long-chain mercaptans and ethylene oxide. Many other types ofuseful surface-active agents are available in commerce. Thesurface-active agents, when used, normally comprise from 1 to 15% byweight of the composition.

[0335] Other useful formulations include suspensions of the activeingredient in a relatively non-volatile solvent such as water, corn oil,kerosene, propylene glycol, or other suitable solvents.

[0336] Still other useful formulations for insecticidal applicationsinclude simple solutions of the active ingredient in a solvent in whichit is completely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene, or other organic solvents. Granularformulations, wherein the toxicant is carried on relatively coarseparticles, are of particular utility for aerial distribution or forpenetration of cover crop canopy. Pressurized sprays, typically aerosolswherein the active ingredient is dispersed in finely divided form as aresult of vaporization of a low boiling dispersant solvent carrier, suchas carbon dioxide, propane, or butane, may also be used. Water-solubleor water-dispersible granules are also useful formulations forinsecticidal application of the present compounds. Such granularformulations are free-flowing, non-dusty, and readily water-soluble orwater-miscible. The soluble or dispersible granular formulationsdescribed in U.S. Pat. No. 3,920,442 are useful herein with the presentinsecticidal compounds. In use by the farmer on the field, the granularformulations, emulsifiable concentrates, flowable concentrates,solutions, etc., may be diluted with water to give a concentration ofactive ingredient in the range of say 0.1% or 0.2% to 1.5% or 2%.

[0337] The active insecticidal compounds of this invention may beformulated and/or applied with other insecticides, ftmgicides,nematicides, plant growth regulators, fertilizers, or other agriculturalchemicals. In using an active compound of this invention, whetherformulated alone or with other agricultural chemicals, to controlinsects, an effective amount and concentration of the active compound isapplied to the locus where control is desired. The locus may be, e.g.,the insects themselves, plants upon which the insects feed, or theinsect habitat. When the locus is the soil, e.g., soil in whichagricultural crops have been or will be planted, the composition of theactive compound may be applied to and optionally incorporated into thesoil. For most applications the effective amount may be as low as, e.g.about 10 to 500 g/ha, preferably about 100 to 250 g/ha.

[0338] In a further embodiment of the present invention, several of thecompounds disclosed above have themselves been found to be novel anduseful intermediates in the preparation of the 1,4-disubstituted benzeneinsecticides disclosed and claimed herein.

[0339] Included among these intermediates are those compounds having theformula XII:

[0340] wherein:

[0341] A is —(CH₂)_(n)—U—R²

[0342] wherein

[0343] n is 0 or 1;

[0344] U is —C(O)—, —CH₂—, oxygen, or —NR⁵, where R⁵ is selected fromthe group consisting of hydrogen, hydroxy, alkyl, sulfonylalllyl,cabonylamino, and carbonylalkyl;

[0345] R² is selected from hydrogen, halo, hydroxy, and 1-R⁴, wherein:

[0346] R⁴ is

[0347] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy;

[0348] R is —T—(CH₂)_(m)—R¹, where

[0349] T is selected from the group consisting of oxygen, nitrogen, andsulfur;

[0350] m is 0, 1, 2, 3, or 4;

[0351] R¹ is hydrogen, halo, alkyl, or —N(R⁸)(R⁹); where R⁸ and R⁹ areindependently selected from the group consisting of hydrogen, alkyl,acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and—(CH₂)_(p)—N(R¹⁶)(R¹⁷), where

[0352] p is 1 or 2;

[0353] R¹⁶ and R¹⁷ are independently selected from the group consistingof hydrogen, alkyl, alkoxyalkyl, and aminoalkyl.

[0354] Some preferred intermediates of formula XII are those in which: nis 1; U is oxygen; R² is 1-R⁴, wherein:

[0355] R⁴ is

[0356] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alknyl, haloalkyl, haloaLkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy;

[0357] T is oxygen or sulfur;

[0358] m is 2; and

[0359] R¹ is halo;

[0360] Additional preferred intermediates of formula XII are those inwhich n is 1; U is —CH₂—; R² is 1-R⁴, wherein:

[0361] R⁴ is

[0362] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy;

[0363] T is oxygen;

[0364] m is 0; and

[0365] R¹ is hydrogen or alkyl.

[0366] Preferred intermediates of formula XII also include thosecompounds in which n is 0; U is —C(O); R² is hydrogen; T is oxygen; m is2; and R¹ is —N(R⁸)(R⁹), where R⁸ and R⁹ are alkyl as well as those inwhich n is 0; U is —CH₂—; R² is halo or hydroxy; T is oxygen; m is 2;and R¹ is —N(R⁸)(R⁹); where R⁸ and R⁹ are alkyl.

[0367] In addition to the compounds set forth above, compounds offormula UU, described generally in Schema 3 above and in greater detailbelow, have also been found to be novel and useful intermediates in thepreparation of the 1,4-disubstituted benzene insecticides disclosed andclaimed herein:

[0368] where X, Y, and Z are independently selected from the groupconsisting of hydrogen, halogen, cyano, nitro, amino, azido, carboxyl,alkyl, alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy; T is selected from the groupconsisting of oxygen, nitrogen, and sulfur; and R¹⁸ is alkyl.

[0369] While the invention has been described in detail and withreference to specific embodiments thereof, it will be apparent to oneskilled in the art that various changes and modifications can be madetherein without departing from the spirit and scope thereof. TABLE 1Insecticidal Optionally Substituted Benzenes

Formula I (FI) —T—(CH₂)_(m)—R¹ —(CH₂)_(n)—U—R² Formula II (FII) FormulaIII (FIII)

R³ R⁴ Formula I A and D are H; R is FII; T is O; m is 2; R¹ is N(C₂H₅)₂Cmpnd No. B n U R² X Y Z  1 2-FIII 1 N 1-R⁴ 4-Cl H H  2 3-FIII 1 N 1-R⁴4-Cl H H Formula I B and D are H; R is FII; T is O; m is 2; R¹ isN(C₂H₅)₂ Cmpnd No. A  3

 4

 5

 6

 7

Formula I A is FIII; B and D are H; R is FII; T is O; m is 2; R¹ isN(C₂H₅)₂; n is 1 Cmpnd No. U R²  8 O

 9 O

 10 O

 11 O

 12 O

 13 N

 14 N

 15 N

 16 N

 17 N

 18 N

 19 N

 20 N

 21 O

 22 O

 23 O

 24 O

 25 O

 26 O

 27 O

 28 O

 29 O

 30 O

 31 O

 32 O

 33 O

 34 O

 35 O

 36 O

 37 O

 38 N

 38 O

Formula I A is FIII; B and D are H; n is 1; U is N; R² is 1-R⁴; X is4-Cl; Y and Z are H Cmpnd No. R  39 —N(C₂H₅)₂  40

 41

 42

Formula I A is FIII; B and D are H; R is FII; T is O; n is 0; R² is1-R⁴; Y and Z are H Cmpnd No. m R¹ U X  43 0 CH₃ C₂H₄ 4-Br  44 0 CH₃

4-Cl  45 1 1-C₆H₅ —OC₂H₄O— 4-Cl  46 1

—CH═N— 4-Cl  47 2 N(C₂H₅)₂ —OC₂H₄O— 4-Cl  48 2 N(C₂H₅)₂

4-Cl  49 2 N(C₂H₅)₂ —NHC₂H₄— 4-Cl  50 2 N(C₂H₅)₂ OCH₂ 4-Cl  51 N(C₂H₅)₂O 4-Cl  52 N(C₂H₅)₂ CH₂ 4-Cl  53 N(C₂H₅)₂ SO₂ 4-Cl  54 N(C₂H₅)₂ CO 4-Cl 55 N(C₂H₅)₂ CF₂ 4-Cl  56 N(C₂H₅)₂ —CH(OH) 4-Cl  57 N(C₂H₅)₂ —CH₂S— 4-Cl 58 N(C₂H₅)₂ CH₂SO 4-Cl  59 N(C₂H₅)₂ CH₂SO₂ 4-Cl  60 2 —OC₂H₅ —CH₂NH—4-Cl Formula I A is FIII; B and D are H; R is FII; T is O; m is 1; n is1; R² is 1-R⁴; X is 4-Cl; Y and Z are H Cmpnd No. U R¹  61 O —CH₂═C(Cl)₂ 62 N —C(O)O  63 N

Formula I A is FIII; B and D are H; R is FII; n is 1; R² is 1-R⁴; CmpndNo. m T U R¹ X Y Z  64 1 O N —CH₃ 4-Cl H H  65 1 O N —CH₂F 4-Cl H H  661 O O

4-Cl H H  67 1 O O

4-Cl H H Hydrochloride Salt  68 1 O O

4-Cl H H  69 1 O O

4-Cl H H  70 1 O O

4-Cl H H  71 2 S N —N(C₂H₅)₂ 4-Cl H H  72 2 O CH₂ —N(C₂H₅)₂ 4-Br H H  732 O CH₂ —N(C₂H₅)₂ 4-Cl H H  74 2 O N —N(CH₃)₂ H H H  75 2 O N —N(C₂H₅)₂H H H  76 2 O N

H H H  77 2 O N —N(CH₃)₂ 4-Br H H  78 2 O N —N(C₂H₅)₂ 4-Br H H  79 2 O N—N(isopropyl)₂ 4-Br H H  80 2 O N

4-Br H H  81 2 O N

4-Br H H  82 2 O N —NH(C₂H₅) 4-Cl H H  83 2 O N —N(CH₃)₂ 4-Cl H H  84 2O N —N(C₂H₅)₂ 4-Cl H H  85 2 O N —N(C₂H₅)₂ 4-Cl H H Chloride Salt  86 2O N —N(C₂H₅)₂ 8-Cl H H  87 2 O N —N(isopropyl)₂ 4-Cl H H  88 2 O N—N(C₄H₉)₂ 4-Cl H H  89 2 O N

4-Cl H H  90 2 O N

4-Cl H H  91 2 O N

4-Cl H H  92 2 O N

4-Cl H H  93 2 O N

4-Cl H H  94 3 O N —N(CH₃)₂ 4-Cl H H  95 3 O N —N(C₄H₉)₂ 4-Cl H H  96 3O N

4-Cl H H  97 4 O N —N(C₄H₉)₂ 4-Cl H H  98 2 O O

4-Cl H H  99 2 O O

4-Cl H H 100 2 O O

4-Cl H H 101 2 O O

4-Cl H H 102 2 O O

4-Cl H H 103 2 O O

4-Cl H H 104 2 O O

4-Cl H H 105 2 O O

4-Cl H H 106 2 O O

4-Cl H H 107 2 O O

4-Cl 6-Cl H 108 2 O O

4-Cl H H 109 2 O O

4-Cl H H 110 2 O O

4-Cl H H 111 2 O O

4-Cl H H 112 2 O O

4-Cl H H 113 2 O O

4-Cl H H 114 2 O O

4-Cl H H 115 2 O O

4-Cl H H 116 2 O O

4-Cl H H 117 2 O O

4-Cl H H 118 2 O O

4-Cl H H 119 2 O O

4-Cl H H 120 2 O O

4-Cl H H 121 2 O O

4-Cl H H 122 2 O O

4-Cl H H 123 2 O O

4-Cl H H 124 2 O O

4-Cl H H 125 2 O O

4-Cl H H 126 2 O O

4-Cl H H 127 2 O O

4-Cl H H 128 2 O O

4-Cl H H 129 2 O O

4-Cl H H 130 2 O O

4-Cl H H 131 2 O O

4-Cl H H 132 2 O O

4-Cl H H 133 2 O O

4-Cl H H 134 2 O O

4-Cl H H 135 2 O O

4-Cl H H 136 2 O O

4-Cl H H 137 2 O O

4-Cl H H 138 2 O O

4-Cl H H 139 2 O O

4-Cl H H 140 2 O O

4-Cl H H 141 2 O O

4-Cl H H 142 2 O O

5-Cl 6-Cl H 143 2 O O

4-Cl H H 144 2 O O

4-Cl H H 145 2 O O

4-Cl H H 146 2 O O

4-Cl H H 147 2 O O

4-Cl H H 148 2 O O

4-Cl H H 149 2 O O

4-Cl H H 150 2 O O

4-Cl H H 151 2 O O

4-Cl H H 152 2 O O

4-Cl H H 153 2 O O

4-Cl H H 154 2 O O

4-Cl H H 155 2 O O

4-Cl H H 156 2 O O

4-Cl H H 157 2 O O

4-Cl H H 158 2 O O

4-Cl H H 159 2 O O

4-Cl H H 160 2 O O

4-Cl H H 161 2 O O

4-Cl H H 162 2 O O

4-Cl H H 163 2 O O

4-Cl H H 164 2 O O

4-Cl H H 165 2 O O

4-Cl H H 166 2 O O

4-Cl H H 167 2 O O

4-Cl H H 168 2 O O

4-Cl H H 169 2 O O

4-Cl H H 170 2 O O

4-Cl H H 171 2 O O

4-Cl H H 172 2 O O

4-Cl H H 173 2 O O

4-Cl H H 174 2 O O

4-Cl H H 175 2 O O

4-Cl H H 176 2 O O

4-Cl H H 177 2 O O —OC₄H₉ 4-Cl H H 178 2 O O —N(C₂H₅)(OCH₃) 4-Cl H H 1792 O O —N(C₂H₅)₂(OCH₃) 4-Cl H H 180 2 O O —NHC₆H₅ 4-Cl H H 181 2 O O

4-Cl 6-Cl H 182 2 O O

4-Cl 6-Cl H Hydrochloride Salt 183 2 O O

5-Cl 6-Cl H 184 2 O O —NH(C₂H₅) 4-Cl H H 185 2 O O —NH(C₂H₅) 4-Cl H HHydrochloride Salt 186 2 O O —N(C₂H₅)₂ 2-Cl H H 187 2 O O —N(C₂H₅)₂ 3-ClH H 188 2 O O —N(C₂H₅)₂ 4-Cl H H 189 2 O O —N(C₂H₅)₂ 4-Cl H H ChlorideSalt 190 2 O O —N(C₂H₅)(CH₃)₂ 4-Cl H H Iodide Salt 191 2 O O—N(CH₂CN(C₂H₅) 4-Cl H H 192 2 O O —N(C₂H₅)(CH₃) 4-Cl H H 193 2 O O—N(C₂H₅)(CH₃) 4-Cl H H Hydrochloride Salt 194 2 O O —NHtBu 4-Cl H H 1952 O O —N(C₃H₆)(OC₂H₅) 4-Cl H H 196 2 O O —N(CH₂CH═CH₂)₂ 4-Cl H H 197 2 OO —NCH₂C(OCH₃)₂ 4-Cl H H 198 2 O O —NC₃H₆OCH₃ 4-Cl H H 199 2 O O —NC₄H₉4-Cl H H 200 2 O O —N(CH₃)C₂H₄CN 4-Cl H H 201 2 O O —N(C₂H₅)C₄H₉ 4-Cl HH 202 2 O O —N(C₄H₉)₂ 4-Cl H H 203 2 O O —N(isopropyl)₂ 4-Cl H H 204 2 OO —N(C₆H₁₃)₂ 4-Cl H H 205 2 O O —N(CH₃)C₁₇H₃₅ 4-Cl H H 206 2 O O—N(C₂H₅)₂ 5-Cl H H 207 2 O O —N(C₂H₅)₂ 6-Cl H H 208 2 O O —N(C₂H₅)₂ 7-ClH H 209 2 O O —N(C₂H₅)₂ 8-Cl H H 210 2 O O —N(C₂H₅)₂ 2-Cl 4-Cl H 211 2 OO —N(C₂H₅)₂ 2-Cl 5-Cl H 212 2 O O —N(C₂H₅)₂ 2-Cl 6-Cl H 213 2 O O—N(C₂H₅)₂ 2-Cl 8-Cl H 214 2 O O —N(C₂H₅)₂ 4-Cl 5-Cl 6-Cl 215 2 O O—N(C₂H₅)₂ 4-Cl 5-Cl H 216 2 O O —N(C₂H₅)₂ 4-Cl 6-Cl H 217 2 O O—N(C₂H₅)₂ 4-Cl 6-Cl H Chloride Salt 218 2 O O —N(C₂H₅)₂ 4-Cl 6-Cl HSulfonic Salt 219 2 O O —N(C₂H₅)₂ 4-Cl 6-Cl H Trifluoroacetic Salt 220 2O O —N(C₂H₅)₂ 4-Cl 6-Cl H Methylbenzenesulfonic Salt 221 2 O O —N(C₂H₅)₂4-Cl 7-Cl H 222 2 O O —N(C₂H₅)₂ 4-Cl 8-Cl H 223 2 O O —N(C₂H₅)₂ 5-Cl6-Cl H 224 2 O O —N(C₂H₅)₂ 5-Cl 6-Cl H Chloride salt 225 2 O O —N(C₂H₅)₂5-Cl 6-Cl H Phosphoric salt 226 2 O O —NHtBu 5-Cl 6-Cl H 227 2 O O—N(C₂H₅)₂ 6-Cl 8-Cl H 228 2 O O —N(C₂H₅)₂ 4-Br H H 229 2 O O —N(C₂H₅)₂6-Br H H 230 2 O O —N(C₂H₅)₂ 5-Br H H 231 2 O O —N(C₂H₅)₂ 4-F H H 232 2O O —N(C₂H₅)₂ 4-CF₃ H H 233 2 O O —N(C₂H₅)₂ 6-CF₃ H H 234 2 O O—N(C₂H₅)₂ 4-N₃ H H 235 2 O O —N(C₂H₅)₂ 4-OCH₃ H H 236 2 O O —N(C₂H₅)₂4-OCH₃ H H Chloride Salt 237 2 O O —N(C₂H₅)₂ 5-OCH₃ H H 238 2 O O—N(C₂H₅)₂ 4-NO₂ H H 239 2 O O —N(C₂H₅)₂ 4-CN H H 240 2 O O —N(C₂H₅)₂2-CH₃ H H 241 2 O O —N(C₂H₅)₂ 6-CH₃ H H 242 2 O O —N(C₂H₅)₂

H H 243 2 O O —N(C₂H₅)₂

H H 244 2 O O —N(C₂H₅)₂ 5-Cl 6-CF₃ H 245 2 O O —N(C₂H₅)₂ 5-Cl 6-Br H 2462 O O —N(C₂H₅)₂ 5-Cl 6-I H 247 2 O O —N(C₂H₅)₂ 5-I 6-Cl H 248 2 O O—N(C₂H₅)₂ 5-Cl 6-OCF₃ H 249 2 O O —N(C₂H₅)₂ 5-Cl 6-CN H 250 2 O O—N(C₂H₅)₂ 5-Cl 6-NO₂ H 251 2 O O —N(C₂H₅)₂ 5-CF₃ 6-Cl H 252 2 O O—N(C₂H₅)₂ 5-OCH₃ 6-Cl H 253 2 O O —N(C₂H₅)₂ 4-CF₃ 6-Cl H 254 2 O O

5-Cl 6-Cl H 255 2 O CH₂

5-Cl 6-Cl H 256 2 O O

5-Cl 6-Cl H 257 2 O S —N(C₂H₅)₂ 5-Cl 6-Cl H 258 2 O SO₂ —N(C₂H₅)₂ 5-Cl6-Cl H 259 3 O O —N(C₂H₅)₂ 4-Cl H H 260 4 O O —N(C₂H₅)₂ 4-Cl H H Pleasenote that Compound No. 261 is a mixture of Compound 212 and(2-(4-((2,4,6- trichloronaphthyloxy)methyl)phenoxy)ethyl)diethylamine.Formula I A is FIII; R is FII; T is O; m is 2; R¹ is —N(C₂H₅)₂; R² is1-R⁴; X is 4-Cl; Y and Z are H Cmpnd No. B D n U 262 2-F H 1 N 2632-OCH₃ H 1 N 264 3-OCH₃ H 1 N 265 3-OCH₃ 5-OCH₃ 1 N 2665-(OC₂H₄N(C₂H₅)₂) H 1 N 267 2-Cl H 1 N 268 3-Cl H 1 N 269 2-Cl 3-Cl 1 N270 2-Cl 6-Cl 1 N 271 3-Cl 5-Cl 1 N 272 3-Cl 5-Cl 0

Formula I A and D are H; R is FII; T is O; m is 2; R¹ is N(C₂H₅)₂ CmpndNo. B n U R² J L W 273 5-FIII 1 N 1-R³ 4-Cl H H 274 6-FIII 1 N 1-R³ 4-ClH H Formula I A is FIII; B and D are H; R is FII; T is O; m is 2; n is1; U is O Cmpnd No. R¹ R² 275

276

277 —N(C₂H₅)₂

Formula I A is FIII; B and D are H; R is FII; m is 2; T is O; R¹ is—N(C₂H₅)₂; n is 1; R² is 1-R³; mpnd No. U J L W 278 N H H H 279 N 2-OCF₃H H 280 N 4-OCF₃ H H 281 N 2-OC₆H₅ H H 282 N 3-OC₆H₅ H H 283 N 2-Cl H H284 N 4-Cl H H 285 N 2-Cl 3-Cl H 286 N 2-Cl 3-Cl 4-Cl 287 N 2-Cl 4-Cl H288 N 2-Cl 4-Cl 5-Cl 289 N 3-Cl 4-Cl H 290 N 3-Cl 5-Cl H 291 N 2-C₆H₅ HH 292 N 2-C₆H₅ 4-Cl H 293 N 3-C₆H₅ 4-Cl H 294 N 2-F 3-F H 295 N 2-F 3-F4-F 296 N 2-F 4-F H 297 N 2-F 4-F 5-F 298 N 2-CH₃ 3-CH₃ H 299 N 2-CH₃4-CH₃ H 300 N 2-OCH₃ 4-OCH₃ H 301 N 2-OCH₃ 5-OCH₃ H 302 N 3-OCH₃ 5-OCH₃H 303 O 3-OCH₃ 5-OCH₃ H 304 O H H H 305 O 2-Cl H H 306 O 4-Cl H H 307 O2-Cl 3-Cl H 308 O 2-Cl 3-Cl 4-Cl 309 O 2-Cl 4-Cl H 310 O 2-Cl 4-Cl 5-Cl311 O 2-Cl 5-Cl H 312 O 2-Cl 6-Cl H 313 O 3-Cl 4-Cl H 314 O 3-Cl 5-Cl H315 O 2-Cl 4-Br H 316 O 2-Cl 6-Br H 317 O 2-Cl 5-CH₃ H 318 O 2-C(CH₃)₃ HH 319 O 3-C(CH₃)₃ H H 320 O 4-C(CH₃)₃ H H 321 O 2-isopropyl H H 322 O4-C₃H₇ H H 323 O 4-OCH₃ H H 324 O 4-OCF₃ H H 325 O 2-CN H H 326 O 5-CN HH 327 O 2-NC(O)CH₃ H H 328 O 2-C(O)OC₂H₅ H H 329 O 4-C(O)CH₃ H H 330 O2-C(O)CH₃ 3-OCH₃ H 331 O 2-C(O)CH₃ 4-OCH₃ H 332 O 2-CH₃ 4-Cl H 333 O3-CH₃ 4-Cl H 334 O 2-NO₂ 4-Cl H 335 O

4-Cl H 336 O

4-Cl 5-CH₃ 337 O 2-CH₃ 4-CH₃ H 338 O 2-CH₃ 3-CH₃ 5-CH₃ 339 O 2-CH₃ 3-CH₃6-CH₃ 340 O 2-OCH₃ 4-CH₃ H 341 O 2-Br 4-Br H 342 O 2-Br 6-Br H 343 O2-Br 4-CH₃ H 344 O 2-Br 4-CH₃ 6-Br 345 O 2-F 3-F H 346 O 2-F 5-F H 347 O2-F 6-F H 348 O 3-F 5-F H 349 O 4-F 6-F H 350 O 3-F 4-F 6-F 351 O 3-CF₃H H 352 O 2-CF₃ 5-CF₃ H Formula I A is FIII; B and D are H; n is 1; U isO; R² is 1-R⁴ Cmpnd No. R X Y Z 353

4-Cl H H 354

4-Cl 6-Cl H 355

5-Cl 6-Cl H 356

5-Cl 6-Cl H 357

5-Cl 6-Br H 360

5-Cl 6-Cl H 361

5-Cl 6-Cl H 362

5-Cl 6-Cl H 363

4-Cl 6-Cl H 364

5-Cl 6-Cl H 365

5-Cl 6-Cl H 366

5-Cl 6-Cl H 367

5-Cl 6-Cl H 368

5-Cl 6-Cl H 369

5-Cl 6-Cl H 370

5-Cl 6-Cl H 371

5-Cl 6-Cl H Formula I A is FIII; B and D are H; R is FII; T is O; n is1; R² is 1-R⁴; Z is H Cmpnd No. m n R¹ X Y U 372 0 1

5-Cl 6-Cl O 373 0 1

5-Cl 6-Cl O 374 0 1

4-Cl H O 375 0 1

4-Cl H O 376 1 1

5-Cl 6-Cl O 377 1 1

5-Cl 6-Cl O 378 1 1

5-Cl 6-Cl O 379 2 O —N(C₂H₅)₂ 4-Cl H —CH₂OCH₂

[0370] TABLE 2 Characterizing Data Melting Point/ Cmpd No EmpiricalFormula Physical State 1 C₂₃H₂₇ClN₂O OIL 2 C₂₃H₂₇ClN₂O OIL 3 C₂₀H₃₃N₃O₃OIL 4 C₂₃H₂₉ClN₂O OIL 5 C₂₄H₃₀ClN₃O₂ OIL 6 C₂₄H₂₉ClN₂O OIL 7C₂₃H₂₅ClN₂O₂ SOLID 8 C₂₄H₂₈ClNO₂ SOLID 9 C₂₂H₂₆N₂O₂ SOLID 10C₂₃H₂₅F₃N₂O₂ SOLID 11 C₂₂H₂₅ClN₂O₂ OIL 12 C₂₂H₂₅FN₂O₂ OIL 13 C₂₃H₂₈N₂OOIL 14 C₂₂H₂₇N₃O LIQUID 15 C₂₂H₂₇N₃O LIQUID 16 C₂₂H₂₇N₃O SOLID 17C₂₃H₃₁ClN₂O₂ OIL 18 C₁₈H₂₄ClN₃O LIQUID 19 C₂₄H₃₂ClN₃O₂  93-95° C. 20C₂₃H₃₁ClN₂O OIL 21 C₂₅H₂₇NO₃ SOLID 22 C₂₁H₂₅N₃O₂ OIL 23 C₂₁H₂₄ClN₃O₂ OIL24 C₁₃H₈F₅NO₂S 39 C₂₁H₂₃ClN₂ OIL 40 C₂₅H₃₀ClN₃O OIL 41 C₂₈H₃₆ClN₃O₂ FOAM43 C₁₉H₁₇BrO OIL 44 C₁₈H₁₅ClN₂O₂ 220° C. > 45 C₂₅H₂₁ClO₃ 106-107° C. 46C₂₃H₂₃ClN₂O₂ OIL 47 C₂₄H₂₈ClNO₃ OIL 48 C₂₃H₂₆ClN₃O₂ 210° C. > 49C₂₅H₃₁ClN₂O OIL 60 C₂₁H₂₂ClNO₂ OIL 61 C₂₀H₁₅Cl₃O₂ SOLID 62 C₁₉H₁₆ClNO₃ 90-92° C. 63 C₂₃H₂₅ClN₂O₂ 123-125° C. 64 C₁₉H₁₈ClNO  92-93° C. 65C₁₉H₁₇ClFNO SOLID 66 C₂₀H₁₇ClN₄O₂ 122-124° C. 67 C₁₉H₁₆ClN₄O₂.Cl SOLID68 C₂₀H₁₇ClN₄O₂ 159-161° C. 69 C₂₁H₁₉ClN₄O₂ 104-106° C. 70 C₂₁H₁₉ClN₄O₂SOLID 71 C₂₃H₂₇ClN₂S OIL 72 C₂₄H₂₈BrNO OIL 73 C₂₄H₂₈ClNO OIL 74C₂₁H₂₄N₂O LIQUID 75 C₂₃H₂₈N₂O OIL 76 C₂₃H₂₆N₂O₂ SOLID 77 C₂₁H₂₃BrN₂OLIQUID 78 C₂₃H₂₇BrN₂O SOLID 79 C₂₅H₃₁BrN₂O SOLID 80 C₂₃H₂₅BrN₂O₂ SOLID81 C₂₃H₂₅BrN₂O SOLID 82 C₂₁H₂₃ClN₂O 184-187° C. 83 C₂₁H₂₃ClN₂O LIQUID 84C₂₃H₂₇ClN₂O OIL 85 C₂₃H₂₇ClN₂O.ClH 86 C₂₃H₂₇ClN₂O PASTE 87 C₂₅H₃₁ClN₂OSOLID 88 C₂₇H₃₅ClN₂O LIQUID 89 C₂₃H₂₅ClN₂O₂ SOLID 90 C₂₃H₂₅ClN₂O SOLID91 C₂₂H₂₃ClN₂O₃ 102-104° C. 92 C₂₄H₂₇ClN₂O₃ OIL 93 C₂₄H₂₇ClN₂O SOLID 94C₂₂H₂₅ClN₂O SOLID 95 C₂₈H₃₇ClN₂O LIQUID 96 C₂₄H₂₇ClN₂O₂ LIQUID 97C₂₉H₃₉ClN₂O LIQUID 98 C₂₅H₂₇ClO₂ LIQUID 99 C₂₅H₂₈ClNO₂ SOLID 100C₂₅H₂₆ClNO₂ SOLID 101 C₂₄H₂₆ClNO₂  89-90° C. 102 C₂₅H₂₈ClNO₂ OIL 103C₂₅H₂₈ClNO₂ OIL 104 C₂₅H₂₈ClNO₂ OIL 105 C₂₆H₃₀ClNO₂  60-65° C. 106C₂₆H₃₀ClNO₂ OIL 107 C₂₆H₂₉Cl₂NO₂ OIL 108 C₂₇H₃₀ClNO₄  85-87° C. 109C₃₀H₃₀ClNO₂  89-91° C. 110 C₃₁H₃₀ClNO₃ 112-115° C. 111 C₃₁H₃₂ClNO₂ 88-91° C. 112 C₂₅H₂₈ClNO₂ SOLID 113 C₂₃H₂₅ClN₂O₂ OIL 114 C₂₆H₂₉ClN₂O₄OIL 115 C₂₉H₂₉ClN₂O₂ OIL 116 C₃₀H₂₉ClN₂O₃ OIL 117 C₃₀H₃₁ClN₂O₂  71-73°C. 118 C₂₃H₂₄ClNO₂S OIL 119 C₂₅H₂₈ClNO₃ OIL 120 C₂₅H₂₈ClNO₃ OIL 121C₂₈H₂₈ClNO₂ LIQUID 122 C₂₆H₃₂ClNO₂  88-90° C. 123 C₂₆H₃₂ClNO₂ OIL 124C₂₆H₃₀ClNO₂ OIL 125 C₂₆H₃₀ClNO₂ OIL 126 C₂₄H₂₆ClNO₂ SEMI SOLID 127C₂₉H₃₅ClN₂O₂  91-92° C. 128 C₂₈H₂₆ClNO₂ SYRUP 129 C₂₉H₃₁ClN₂O₂ SYRUP 130C₂₇H₂₃ClF₃NO₃ SYRUP 131 C₂₃H₂₆ClNO₂  58-59° C. 132 C₂₇H₃₂ClNO₂ OIL 133C₂₅H₂₃ClN₂O₂ OIL 134 C₂₈H₂₈ClNO₄  96-98° C. 135 C₂₈H₃₄ClNO₂ OIL 136C₂₇H₂₆ClNO₃  95-96° C. 137 C₂₆H₂₃Cl₂NO₂  87-88° C. 138 C₃₀H₃₇ClN₂O₂ OIL139 C₂₇H₂₆ClNO₂ OIL 140 C₂₈H₃₄ClNO₂ OIL 141 C₂₃H₂₄ClNO₂  75-77° C. 142C₂₃H₂₃Cl₂NO₂ 152-154° C. 143 C₂₇H₃₂ClNO₂ OIL 144 C₂₂H₂₂ClNO₂S  83-86° C.145 C₂₈H₃₂ClNO₂ OIL 146 C₂₆H₃₀ClNO₂ OIL 147 C₂₆H₃₀ClNO₂ OIL 148C₂₆H₃₀ClNO₂ OIL 149 C₃₀H₂₇ClN₂O₂ 131-135° C. 150 C₂₃H₂₂ClNO₂ OIL 151C₂₉H₂₇ClN₂O₂ OIL 152 C₃₀H₂₉ClN₂O₃ 133-136° C. 153 C₃₀H₃₁ClN₂O₃ OIL 154C₂₄H₂₄ClNO₂  90-91° C. 155 C₃₀H₂₈ClF₃N₂O₂  80-82° C. 156 C₂₉H₂₈ClFN₂O₂120-121° C. 157 C₃₁H₃₁ClN₂O₃ OIL 158 C₃₆H₃₄Cl₂N₂O₂ OIL 159 C₂₇H₃₀ClNO₄OIL 160 C₂₉H₃₅ClN₂O₃ OIL 161 C₃₀H₃₀ClNO₃ 123-125° C. 162 C₂₈H₂₈ClN₃O₂OIL 163 C₂₇H₂₇ClN₂O₂ OIL 164 C₂₉H₂₈ClN₃O₄ 164-166° C. 165 C₂₆H₃₁ClN₂O₂ 83-89° C. 166 C₂₅H₃₁ClN₂O₂ OIL 167 C₂₉H₃₅ClN₂O₂ 135-140° C. 168C₂₈H₃₂ClNO₂ OIL 169 C₂₇H₂₇ClN₂O₂ OIL 170 C₂₈H₂₈ClNO₂ OIL 181C₂₃H₂₅Cl₂NO₃ OIL 183 C₂₃H₂₅Cl₂NO₃  81-87° C. 184 C₂₁H₂₂ClNO₂ LIQUID 185C₂₁H₂₃ClNO₂.Cl 201-203° C. 186 C₂₃H₂₆ClNO₂ LIQUID 187 C₂₃H₂₆ClNO₂ OIL188 C₂₃H₂₆ClNO₂ OIL 189 C₂₃H₂₆ClNO₂.ClH SOLID 190 C₂₃H₂₇ClNO₂.I LIQUID191 C₂₃H₂₃ClN₂O₂ LIQUID 192 C₂₂H₂₄ClNO₂ SOLID 193 C₂₂H₂₅ClNO₂.Cl SOLID194 C₂₃H₂₆ClNO₂  84-85° C. 195 C₂₄H₂₈ClNO₃ SYRUP 196 C₂₅H₂₆ClNO₂ OIL 197C₂₃H₂₆ClNO₄ OIL 198 C₂₃H₂₆ClNO₃ SEMI-SOLID 199 C₂₃H₂₆ClNO₂ 138-145° C.200 C₂₃H₂₃ClN₂O₂ OIL 201 C₂₅H₃₀ClNO₂ OIL 202 C₂₇H₃₄ClNO₂ OIL 203C₂₅H₃₀ClNO₂ OIL 204 C₃₁H₄₂ClNO₂ OIL 205 C₃₈H₅₆ClNO₂  63-64° C. 206C₂₃H₂₆ClNO₂ LIQUID 207 C₂₃H₂₆ClNO₂ LIQUID 208 C₂₃H₂₆ClNO₂ OIL 209C₂₃H₂₆ClNO₂ LIQUID 210 C₂₃H₂₅Cl₂NO₂ OIL 211 C₂₃H₂₅Cl₂NO₂ OIL 213C₂₃H₂₅Cl₂NO₂ LIQUID 214 C₂₃H₂₄Cl₃NO₂ SOLID 215 C₂₃H₂₅Cl₂NO₂ LIQUID 216C₂₃H₂₅Cl₂NO₂ OIL 217 C₂₃H₂₅Cl₂NO₂.ClH 200° C. > 218 C₂₃H₂₅Cl₂NO₂.CH₄O₃SSOLID 219 C₂₃H₂₅Cl₂NO₂.C₂HF₃O₂ SOLID 220 C₂₃H₂₅Cl₂NO₂.C₇H₈O₃S SOLID 221C₂₃H₂₅Cl₂NO₂ PASTE 222 C₂₃H₂₅Cl₂NO₂ PASTE 223 C₂₃H₂₅Cl₂NO₂ OIL 224C₂₃H₂₆Cl₂NO₂.Cl 204-206° C. 225 C₂₃H₂₅Cl₂NO₂.H₃O₄P SOLID 226C₂₃H₂₅Cl₂NO₂ 215-217° C. 227 C₂₃H₂₅Cl₂NO₂ OIL 228 C₂₃H₂₆BrNO₂ OIL 229C₂₃H₂₆BrNO₂ SOLID 230 C₂₃H₂₆BrNO₂ SOLID 231 C₂₃H₂₆FNO₂ SOLID 232C₂₄H₂₆F₃NO₂ OIL 233 C₂₄H₂₆F₃NO₂ COLORLESS OIL 234 C₂₃H₂₈N₂O₂ OIL 235C₂₄H₂₉NO₃ OIL 236 C₂₄H₂₉NO₃.ClH SOLID 237 C₂₄H₂₉NO₃ OIL 238 C₂₃H₂₆N₂O₄OIL 239 C₂₄H₂₆N₂O₂ OIL 240 C₂₄H₂₉NO₂ OIL 241 C₂₄H₂₉NO₂ SOLID 242C₂₉H₃₀FNO₂  67-71° C. 243 C₂₉H₃₀ClNO₃ OIL 259 C₂₄H₂₈ClNO₂ LIQUID 260C₂₅H₃₀ClNO₂ LIQUID 261 C₂₃H₂₅Cl₂NO₂.C₂₃H₂₄Cl₃NO₂ LIQUID 262 C₂₃H₂₆ClFN₂OLIQUID 263 C₂₄H₂₉ClN₂O₂ LIQUID 264 C₂₄H₂₉ClN₂O₂ SOLID 265 C₂₅H₃₁ClN₂O₃LIQUID 266 C₂₉H₄₀ClN₃O₂ LIQUID 267 C₂₃H₂₆Cl₂N₂O LIQUID 268 C₂₃H₂₆Cl₂N₂OLIQUID 269 C₂₃H₂₅Cl₃N₂O SOLID 270 C₂₃H₂₅Cl₃N₂O SOLID 271 C₂₃H₂₅Cl₃N₂OSOLID 272 C₂₃H₂₃Cl₃N₂O₂ SOLID 273 C₁₉H₂₅ClN₂O LIQUID 274 C₁₉H₂₅ClN₂OLIQUID 275 C₂₀H₂₅ClN₂O₂ OIL 276 C₂₄H₃₁ClN₂O₄ OIL 277 C₂₀H₂₆ClNO₂ OIL 278C₁₉H₂₆N₂O OIL 279 C₂₀H₂₅F₃N₂O₂ OIL 280 C₂₀H₂₅F₃N₂O₂ OIL 281 C₂₅H₃₀N₂O₂OIL 282 C₂₅H₃₀N₂O₂ OIL 283 C₁₉H₂₅ClN₂O OIL 284 C₁₉H₂₅ClN₂O OIL 285C₁₉H₂₄Cl₂N₂O OIL 286 C₁₉H₂₃Cl₃N₂O OIL 287 C₁₉H₂₄Cl₂N₂O OIL 288C₁₉H₂₃Cl₃N₂O OIL 289 C₁₉H₂₄Cl₂N₂O OIL 290 C₁₉H₂₄Cl₂N₂O OIL 291 C₂₅H₃₀N₂OLIQUID 292 C₂₅H₂₉ClN₂O LIQUID 293 C₂₅H₂₉ClN₂O LIQUID 294 C₁₉H₂₄F₂N₂O OIL295 C₁₉H₂₃F₃N₂O OIL 296 C₁₉H₂₄F₂N₂O OIL 297 C₁₉H₂₃F₃N₂O OIL 298C₂₁H₃₀N₂O OIL 299 C₂₁H₃₀N₂O OIL 300 C₂₁H₃₀N₂O₃ OIL 301 C₂₁H₃₀N₂O₃ OIL302 C₂₁H₃₀N₂O₃ OIL 303 C₂₁H₂₉NO₄ LIQUID 304 C₂₆H₃₁NO₃ SOLID 305C₁₉H₂₄ClNO₂ SOLID 306 C₁₉H₂₄ClNO₂ SOLID 307 C₁₉H₂₃Cl₂NO₂ LIQUID 308C₁₉H₂₂Cl₃NO₂ SOLID 309 C₁₉H₂₃Cl₂NO₂ LIQUID 310 C₁₉H₂₂Cl₃NO₂ LIQUID 311C₁₉H₂₃Cl₂NO₂ LIQUID 312 C₁₉H₂₃Cl₂NO₂ LIQUID 313 C₁₉H₂₃Cl₂NO₂ SOLID 314C₁₉H₂₃Cl₂NO₂ SEMI-SOLID 315 C₁₉H₂₃BrClNO₂ SOLID 316 C₁₉H₂₃BrClNO₂ LIQUID317 C₂₀H₂₆ClNO₂ LIQUID 318 C₂₃H₃₃NO₂ LIQUID 319 C₂₃H₃₃NO₂ SOLID 320C₂₃H₃₃NO₂ LIQUID 321 C₂₂H₃₁NO₂ LIQUID 322 C₂₂H₃₁NO₂ SOLID 323 C₂₀H₂₇NO₃SOLID 324 C₂₀H₂₄F₃NO₃ SOLID 325 C₂₀H₂₄N₂O₂ LIQUID 326 C₂₀H₂₄N₂O₂ LIQUID327 C₂₁H₂₈N₂O₃ SOLID 328 C₂₂H₂₉NO₄ SOLID 329 C₂₁H₂₇NO₃ LIQUID 330C₂₂H₂₉NO₄ LIQUID 331 C₂₂H₂₉NO₄ SOLID 332 C₂₀H₂₆ClNO₂ LIQUID 333C₂₀H₂₆ClNO₂ SOLID 334 C₁₉H₂₃ClN₂O₄ LIQUID 335 C₂₂H₂₅ClN₂O₃ LIQUID 336C₂₃H₂₇ClN₂O₃ LIQUID 337 C₂₁H₂₉NO₂ LIQUID 338 C₂₂H₃₁NO₂ SOLID 339C₂₂H₃₁NO₂ SOLID 340 C₂₁H₂₉NO₃ LIQUID 341 C₁₉H₂₃Br₂NO₂ SOLID 342C₁₉H₂₃Br₂NO₂ LIQUID 343 C₂₀H₂₆Br₂NO₂ LIQUID 344 C₂₀H₂₅Br₂NO₂ SOLID 345C₁₉H₂₃F₂NO₂ SOLID 346 C₁₉H₂₃F₂NO₂ LIQUID 347 C₁₉H₂₃F₂NO₂ LIQUID 348C₁₉H₂₃F₂NO₂ LIQUID 349 C₁₉H₂₃F₂NO₂ LIQUID 350 C₁₉H₂₂F₃NO₂ LIQUID 351C₂₀H₂₄F₃NO₂ LIQUID 352 C₂₁H₂₃F₆NO₂ LIQUID 353 C₂₃H₂₄ClNO₂ SOLID 354C₂₃H₂₄Cl₂N₂O SOLID 355 C₂₃H₂₄Cl₂N₂O SOLID 356 C₂₆H₂₈Cl₂N₂O₃ SOLID 357C₂₃H₂₄BrClN₂O 150-151° C. 358 C₂₇H₃₀Cl₂N₂O 142-145° C. 359 C₂₆H₂₈Cl₂N₂O131-133° C. 360 C₂₃H₂₂Cl₂N₂O 135-137° C. 361 C₂₅H₂₈Cl₂N₂O SOLID 363C₂₄H₂₆Cl₂N₂O SOLID 364 C₂₅H₂₈Cl₂N₂O SOLID 365 C₂₈H₂₅Cl₃N₂O SOLID 366C₂₁H₂₀Cl₂N₂O SOLID 267 C₂₂H₂₂Cl₂N₂O SOLID 368 C₂₄H₂₆Cl₂N₂O SOLID 369C₂₄H₂₆Cl₂N₂O SOLID 370 C₂₃H₂₃Cl₂FN₂O SOLID 371 C₂₇H₂₄Cl₂N₂O SOLID 372C₂₄H₂₇Cl₂NO₂ OIL 373 C₂₇H₃₁Cl₂NO₂ OIL 374 C₂₃H₂₄ClNO₂ SEMI-SOLID 375C₂₄H₂₆ClNO₂ OIL 376 C₂₄H₂₅Cl₂NO₂ OIL 377 C₂₅H₂₇Cl₂NO₂ OIL 378C₂₃H₂₃Cl₂NO₂ SOLID 379 C₂₄H₂₈ClNO₂ SOLID

[0371] TABLE 3 Insecticidal Activity of 1,4-Disubstituted BenzenesIncorporated into the Diet (SRTD) of Tobacco Budworm Rate of PercentGrowth Percent Cmpd No. Application¹ Inhibition² Mortality³ 8 4.6 11 —10 4.6 35 — 20 5.6 12 — 21 5.6 20 — 47 4.6 23 — 49 4.6 16 — 66 4.6 9 —68 5.6 16 — 72 5.6 23 — 73 5.6 24 — 5.6 20 — 77 5.6 17 — 78 5.6 12 — 5.60 — 79 6.6 −4 — 80 5.6 12 — 82 5.6 12 — 84 6.6 −20 — 6.6 34 — 5.6 11 —85 6.6 20 — 5.6 15 — 87 6.6 −2 — 88 5.6 1 — 89 5.6 12 — 93 6.6 3 — 944.6 18 — 99 6.6 6 — 100 6.6 6 — 101 6.6 14 — 102 6.6 7 — 103 5.6 25 —104 5.6 21 — 105 4.6 24 — 106 6.6 35 — 107 6.6 17 — 111 5.6 1 — 112 5.626 — 113 5.6 −3 — 114 5.6 0 — 117 5.6 10 — 118 4.6 6 — 121 4.6 12 — 1225.6 23 — 123 5.6 30 — 124 5.6 20 — 125 5.6 18 — 126 6.6 14 — 130 6.6 17— 131 6.6 25 — 132 5.6 27 — 133 4.6 28 — 134 4.6 12 — 135 5.6 24 — 1364.6 33 — 137 4.6 28 — 138 4.6 27 — 139 4.6 26 — 140 5.6 32 — 141 6.6 24— 142 6.6 32 — 143 4.6 22 — 144 4.6 20 — 145 5.6 29 — 146 5.6 25 — 1475.6 33 — 148 5.6 4 — 149 5.6 22 — 150 5.6 12 — 151 5.6 5 — 152 4.6 16 —153 4.6 19 — 154 6.6 27 — 161 5.6 23 — 163 5.6 24 — 166 5.6 24 — 181 6.643 — 183 6.6 28 — 6.6 18 — 184 5.6 43 — 187 4.6 14 — 188 6.6 1 — 6.6 19— 6.6 −1 — 190 5.6 4 — 191 6.6 6 — 192 6.6 2 — 193 6.6 4 — 194 6.6 19 —195 5.6 30 — 196 5.6 20 — 197 4.6 43 — 198 5.6 21 — 199 5.6 9 — 200 5.619 — 201 5.6 13 — 202 5.6 20 — 203 6.6 14 — 206 6.6 12 — 207 6.6 20 —209 6.6 17 — 213 4.6 3 — 214 6.6 18 — 215 6.6 8 — 216 6.6 2 — 6.6 1 —6.6 1 — 6.6 14 — 217 6.6 26 — 6.6 34 — 218 6.6 28 — 219 6.6 16 — 220 6.628 — 221 6.6 13 — 222 6.6 24 — 223 6.6 63 — 7.6 3 — 7.6 17 — 224 6.6 81— 6.6 20 — 6.6 32 — 226 6.6 59 — 227 4.6 7 — 228 6.6 17 — 6.6 5 — 6.6 0— 229 6.6 14 — 230 6.6 12 — 231 5.6 3 — 232 6.6 25 — 6.6 1 — 233 6.6 17— 234 5.6 −3 — 236 4.6 14 — 237 5.6 12 — 238 6.6 22 — 239 5.6 5 — 2415.6 8 — 242 6.6 11 — 243 6.6 10 — 262 4.6 7 — 263 5.6 26 — 264 6.6 19 —267 4.6 7 — 273 5.6 5 — 290 5.6 1 — 306 4.6 −2 — 308 5.6 18 — 313 4.6 37— 350 4.6 21 — 353 3.6 100 100 4.6 100  67 5.6 45 — 6.6 21 — 354 3.6 100100 4.6 100 100 5.6 96  17 6.6 −2 — 355 3.6 100 100 4.6 100 100 5.6 96 17 6.6 −2 — 356 3.6 2 — 4.6 −4 — 357 3.6 100 100 4.6 50  99 5.6 —  15360 3.6 73 — 4.6 11 — 364 4.6 83 — 5.6 −1 — 365 3.6 28 — 4.6 18 — 3663.6 82 — 4.6 47 — 5.6 3 — 367 3.6 100 100 4.6 100 100 5.6 98  33 6.6 25— 368 3.6 100 100 4.6 100 100 5.6 102  50 6.6 36 — 369 3.6 100 100 4.6100 100 5.6 100  83 6.6 28 — 372 3.6 100 100 4.6 100 100 5.6 100 100 6.642 — 373 3.6 100 100 4.6 97  17 5.6 37 — 6.6 −1 — 374 3.6 100 100 4.6 98 50 5.6 41 — 6.6 −1 — 375 3.6 101 100 4.6 85  17 5.6 23 — 376 3.6 100100 4.6 100 100 5.6 89 — 6.6 22 — 377 3.6 100 100 4.6 99  67 5.6 59 —6.6 4 — 378 3.6 100 100 4.6 100 100 5.6 101  83 6.6 48 — 379 3.6 86  334.6 11 —

We claim:
 1. A compound of formula I:

wherein: A is selected from the group consisting of hydrogen; aryl;alkylheterocyclyl; alkenylaminopolycyclyl; alkenylaminoheterocyclyl;alkylaminopolycyclyl; carbonylaminopolycyclyl; where the aryl,heterocyclyl and polycyclyl moieties are optionally substituted with oneor more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl,haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl,haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; andFormula III, where Formula III is —(CH₂)_(n)—U—R² IIIwherein n is 0 or1; U is selected from the group consisting of —CH₂—, —O—CH₂—, oxygen,sulfur, sulfonyl, alkyl, oxyalkyloxy, alkenylamino, cabonylamino and—NR⁵, where R⁵ is selected from the group consisting of hydrogen,hydroxy, alkyl, haloalkyl, sulfonylalkyl, cabonylamino, andcarbonylalkyl; R² is selected from aryl; alkylpolycyclyl; heterocyclyl;polycyclyl; where the aryl, heterocyclyl and polycyclyl moieties areoptionally substituted with one or more of the following: halogen,cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy,carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, or aryl; 1-R³; 1-R⁴; and 2-R⁴, wherein: R³ is

where J, L, and W are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl,alkenyl, alkoxy, haloalkoxy, aminoalkoxy, nitrilyl, carbonyl,alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl,aryl, aryloxy, and heterocyclyl, where the aryl and heterocyclylmoieties may be optionally substituted with halogen, aLkyl, haloalkyl,alkoxy, or haloalkoxy; R⁴ is

where X, Y, and Z are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl,alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, aryloxy, and heterocyclyl, where thephenyl, aryl, and heterocyclyl moieties may be optionally substitutedwith halogen, haloalkyl, haloalkyl, alkoxy, or haloalkoxy; B and D areindependently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy,haloalkoxy, alkoxyaminoalkyl, 2-(Formula III), 3-(Formula III),5-(Formula III), and 6-(Formula III), wherein Formula III, n, U, R², R³,R⁴, R⁵, J, L, W, X, Y, and Z are as defined above; R is —T—(CH₂)_(m)—R¹,—N(R⁶)(R⁷) or heterocyclyl, where the heterocyclyl moiety may beoptionally substituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy,haloalkoxy, alkoxycarbonyl, aryl, alkylaza, arylcarbonyl, benzyl, allyl,propargyl, alkylamino; where the aryl moiety may be optionallysubstituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy,alkoxycarbonyl, aryl, arylcarbonyl; T is selected from the groupconsisting of —CH₂—, carbonyl, oxygen, nitrogen, and sulfur; m is 0, 1,2, 3, or 4; R¹ is selected from the group consisting of —N(R⁸)(R⁹);alkyl; aryl; —C(O)N(R¹²)(R¹³); oxyalkyl; haloalkyl; heterocyclyl;cycloalkyl; —N(O)(R¹⁴)(R¹⁵); —P(O)(R¹⁴)(R¹⁵); —P(S)(R¹⁴)(R¹⁵);alkylamino, where the cycloalkyl, aryl and heterocyclyl moieties may beoptionally substituted with halogen, hydroxy, alkyl, haloalkyl, alkoxy,haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl, alkylamino; where R⁶,R⁷, R⁸, R⁹, R¹², R¹³, R¹⁴ and R¹⁵ are independently selected from thegroup consisting of hydrogen, alkyl, alkoxy, alkylthio, acetyl,alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and—(CH₂)_(p)—N(R¹⁶)(R¹⁷), where p is 1 or 2; R¹⁶ and R¹⁷ are independentlyselected from the group consisting of hydrogen, alkyl, alkoxy,alkoxyalkyl, and aminoalkyl; and the corresponding agriculturallyacceptable salts thereof.
 2. A compound of claim 1 wherein A is selectedfrom the group consisting of hydrogen; alkylaminopolycyclyl;carbonylaminopolycyclyl; where the polycyclyl moieties are optionallysubstituted with one or more of the following: halogen, cyano, nitro,amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl,alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, oraryl; and Formula III, where Formula III is —(CH₂)_(n)—U—R² III whereinn is 0 or 1; U is selected from the group consisting of —CH₂—, oxygen,and 13 NR⁵, where R⁵ is selected from the group consisting of hydrogen,hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl; R² isselected from aryl, alkylpolycyclyl; heterocyclyl; polycyclyl; where thearyl, heterocyclyl and polycyclyl moieties are optionally substitutedwith one or more of the following: halogen, cyano, nitro, amino,carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, carbonyl, alkylcarbonyl,haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and1-R³, wherein R³ is:

where J, L, and W are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl,alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl,haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, andaryloxy, where the aryl moieties may be optionally substituted withhalogen, alkyl, haloalkyl, alkoxy, or haloalkoxy; B and D areindependently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy,haloalkoxy, alkoxyaminoalkyl; R is —T—(CH₂)_(m)—R¹, where T is selectedfrom the group consisting of —CH₂—, oxygen, nitrogen, and sulfur; m is1, 2, 3, or 4; R¹ is —N(R⁸)(R⁹); where R⁸ and R⁹ are independentlyselected from the group consisting of hydrogen, alkyl, alkoxy, acetyl,alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino, and—(CH₂)_(p)—N(R¹⁶)(R¹⁷), where p is 1 or 2; R¹⁶ and R¹⁷ are independentlyselected from the group consisting of hydrogen, alkyl, alkoxy,alkoxyalkyl, and aminoalkyl; and the corresponding agriculturallyacceptable salts thereof.
 3. A compound of claim 2 wherein A is hydrogenor Formula III, where Formula III is —(CH₁)_(n)—U—R² III wherein n is 0or 1; U is selected from the group consisting of —CH₂—, oxygen, and 13NR⁵, where R⁵ is selected from the group consisting of hydrogen,hydroxy, alkyl, sulfonylalkyl, cabonylamino, and carbonylalkyl; R² isselected from heterocyclyl; polycyclyl; where the heterocyclyl andpolycyclyl moieties are optionally substituted with one or more of thefollowing: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl,alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl,alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and 1-R³, wherein R³ is:

where J, L, and W are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl,alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl,haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, andaryloxy, where the aryl moieties may be optionally substituted withhalogen, alkyl, haloalkyl, alkoxy, or haloalkoxy; B and D areindependently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy,haloalkoxy, alkoxyaminoalkyl; T is oxygen or nitrogen m is 2, 3, or 4;R¹ is —N(⁸)(R⁹); where R⁸ and R⁹ are independently selected from thegroup consisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl,alkoxyalkyl, aminoalkyl, carbonylamino, and —(CH₂)_(p)—N(R¹⁶)(R¹⁷),where p is 1 or 2; R¹⁶ and R¹⁷ are independently selected from the groupconsisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl.
 4. Acompound of claim 3 wherein A is Formula III, where Formula III is—(CH₂)_(n)—U—R² III wherein n is 1; U is oxygen or —NR⁵, where R⁵ isselected from the group consisting of hydrogen, hydroxy, alkyl,sulfonylalkyl, cabonylamino, and carbonylalkyl; R² is 1-R³, wherein R³is:

where J, L, and W are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl,alkenyl, alkoxy, haloalkoxy, nitrilyl, carbonyl, alkylcarbonyl,haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, aryl, andaryloxy, where the aryl moieties may be optionally substituted withhalogen, alkyl, haloalkyl, alkoxy, or haloalkoxy; B and D areindependently selected from hydrogen, halogen, alkyl, haloalkyl, alkoxy,haloalkoxy, alkoxyaminoalkyl; T is oxygen or nitrogen m is 2; R¹ is—N(R⁸)(R⁹); where R⁸ and R⁹ are independently selected from the groupconsisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl,alkoxyalkyl, aminoalkyl, carbonylamino, and —(CH₂)_(p)—N(R¹⁶)(R¹⁷),where p is 1 or 2; R¹⁶ and R¹⁷ are independently selected from the groupconsisting of hydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl;
 5. Acompound of claim 1 wherein A is selected from the group consisting ofhydrogen; alkylaminopolycyclyl; and carbonylaminopolycyclyl; where thepolycyclyl moieties are optionally substituted with one or more of thefollowing: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl,alkoxy, haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl,alkoxycarbonyl, haloalkoxycarbonyl, or aryl; and Formula III, whereFormula III is —(CH₂)_(n)—U—R² III wherein n is 0 or 1; U is selectedfrom the group consisting of —CH₂—, oxygen, alkyl, oxyalkyloxy,alkenylamino, cabonylamino and —NR⁵, where R⁵ is selected from the groupconsisting of hydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, andcarbonylalkyl; R² is selected from aryl; alkylpolycyclyl; heterocyclyl;polycyclyl; where the aryl, heterocyclyl and polycyclyl moieties areoptionally substituted with one or more of the following: halogen,cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy,carbonyl, alkylcarbonyl, haloaLkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, or aryl; and 1-R⁴, wherein R⁴ is

where X, Y, and Z are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl,alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy; B and D are independently selectedfrom hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, andalkoxyaminoalkyl; R is —T—(CH₂)_(m)—R¹ or heterocyclyl, where theheterocyclyl moiety may be optionally substituted with halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl,benzyl, allyl, propargyl; T is selected from the group consisting of—CH₂—, oxygen, nitrogen, and sulfur; m is 1, 2, 3, or 4; R¹ is selectedfrom the group consisting of —N(⁸)(R⁹); alkyl; aryl; —C(O)N(R¹²)(R¹³);oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; and —N(O)(R¹⁴)(R¹⁵),where the aryl and heterocyclyl moieties may be optionally substitutedwith halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl,aryl, arylcarbonyl; where R⁸, R⁹, R¹², R¹³, R¹⁴ and R¹⁵ areindependently selected from the group consisting of hydrogen, alkyl,alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino,and —(CH₂)_(p)—N(R¹⁶)(R¹⁷), where p is 1 or 2; R¹⁶ and R¹⁷ areindependently selected from the group consisting of hydrogen, alkyl,alkoxy, alkoxyalkyl, and aminoalkyl; and the correspondingagriculturally acceptable salts thereof.
 6. A compound of claim 5wherein A is hydrogen or Formula III, where Formula III is—(CH₂)_(n)—U—R² III wherein n is 0 or 1; U is selected from the groupconsisting of —CH₂—, oxygen, and —NR⁵, where R⁵ is selected from thegroup consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl,cabonylamino, and carbonylalkyl; R² is selected from alkylpolycyclyl;heterocyclyl; polycyclyl; where the heterocyclyl and polycyclyl moietiesare optionally substituted with one or more of the following: halogen,cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkoxy, haloalkoxy,carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, or aryl; and 1-R⁴, wherein R⁴ is

where X, Y, and Z are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl,allynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, allylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy; B and D are independently selectedfrom hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, andalkoxyaminoalkyl; R is —T—(CH₂)_(m)—R¹ or heterocyclyl, where theheterocyclyl moiety may be optionally substituted with halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl,benzyl, allyl, propargyl; T is selected from the group consisting ofoxygen, nitrogen, and sulfur; m is 1, 2, 3, or 4; R¹ is selected fromthe group consisting of —N(R⁸)(R⁹); alkyl; aryl; —C(O)N(R¹²)(R¹³);oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; and —N(O)(R¹⁴)(R¹⁵),where the aryl and heterocyclyl moieties may be optionally substitutedwith halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl,aryl, arylcarbonyl; where R⁸, R⁹, R¹², R¹³, R¹⁴ and R¹⁵ areindependently selected from the group consisting of hydrogen, alkyl,alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino,and —(CH₂)_(p)—N(R¹⁶)(R¹⁷), where p is 1 or 2; R¹⁶ and R¹⁷ areindependently selected from the group consisting of hydrogen, alkyl,alkoxy, alkoxyalkyl, and aminoalkyl; and the correspondingagriculturally acceptable salts thereof.
 7. A compound of claim 6wherein A is Formula III, where Formula III is —(CH₂)_(n)—U—R² IIIwherein n is 1; U is oxygen or 13 NR⁵, where R⁵ is selected from thegroup consisting of hydrogen, hydroxy, alkyl, sulfonylalkyl,cabonylamino, and carbonylalkyl; R² is 1-R⁴, wherein R⁴ is

where X, Y, and Z are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl,alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy; B and D are independently selectedfrom hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, andalkoxyaminoalkyl; R is —T—(CH₂)_(m)—R¹ or heterocyclyl, where theheterocyclyl moiety may be optionally substituted with halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl,benzyl, allyl, propargyl; T is oxygen or nitrogen; m is 1, 2, 3, or 4;R¹ is selected from the group consisting of —N(R⁸)(R⁹); alkyl; aryl;—C(O)N(R¹²)(R¹³); oxyalkyl; haloalkyl; heterocyclyl; cycloalkyl; and—N(O)(R¹⁴)(R¹⁵), where the aryl and heterocyclyl moieties may beoptionally substituted with halogen, alkyl, haloalkyl, alkoxy,haloalkoxy, alkoxycarbonyl, aryl; arylcarbonyl; where R⁸, R⁹, R¹², R¹³,R¹⁴ and R¹⁵ are independently selected from the group consisting ofhydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl,aminoalkyl, carbonylamino, and —(CH₂)_(p)—N(R¹⁶)(R¹⁷), where p is 1 or2; R¹⁶ and R¹⁷ are independently selected from the group consisting ofhydrogen, alkyl, alkoxy, alkoxyalkyl, and aminoalkyl; and thecorresponding agriculturally acceptable salts thereof.
 8. A compound ofclaim 7 wherein A is Formula III, where Formula III is —(CH₂)_(n)—U—R²III wherein U is oxygen or 13 NR⁵, where R⁵ is hydrogen; R² is 1-R⁴,wherein R⁴ is

where X, Y, and Z are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl,alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy; B and D are independently selectedfrom hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, andalkoxyaminoalkyl; R is —T—(CH₂)_(m)—R¹ or heterocyclyl; where theheterocyclyl moiety may be optionally substituted with halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, aryl, arylcarbonyl,benzyl, allyl, propargyl; T is oxygen or nitrogen; m is 2; R¹ is—N(R⁸)(R⁹) or —N(O)(R¹⁴)(R¹⁵), where R⁸, R⁹, R¹⁴, and R¹⁵ areindependently selected from the group consisting of hydrogen, alkyl,alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl, carbonylamino,and —(CH₂)_(p)—N(R¹⁶)(R¹⁷), where p is 1 or 2; R¹⁶ and R¹⁷ areindependently selected from the group consisting of hydrogen, alkyl,alkoxy, alkoxyalkyl, and aminoalkyl; and the correspondingagriculturally acceptable salts thereof.
 9. A compound of claim 8wherein A is Formula III, where Formula III is —(CH₂)_(n)—U—R²IIIwherein U is O or —NR⁵, where R⁵ is hydrogen; R² is selected from 1-R⁴,wherein R⁴ is

where X, Y, and Z are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl,allynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy; B and D are hydrogen; R is—T—(CH₂)_(m)—R¹; where T is oxygen; R¹ is —N(⁸)(R⁹) or —N(O)(R¹⁴)(R¹⁵),where R⁸, R⁹, R¹⁴, and R¹⁵ are independently selected from the groupconsisting of hydrogen, alkyl, alkoxy, acetyl, alkoxycarbonyl,alkoxyalkyl, aminoalkyl, and carbonylamino; and the correspondingagriculturally acceptable salts thereof.
 10. A compound of claim 9wherein A is Formula III, where Formula III is —(CH₂)_(n)—U—R² IIIwherein U is O; R² is selected from 1-R⁴, wherein R⁴ is

where X, Y, and Z are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl,haloalkyl, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl,alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl,aryl, and aryloxy, where the aryl moieties may be optionally substitutedwith halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy; R¹ is —N(⁸)(R⁹)or —N(O)(R¹⁴)(R¹⁵), where R⁸, R⁹, R¹⁴ and R¹⁵ are alkyl; and thecorresponding agriculturally acceptable salts thereof.
 11. A compound ofclaim 10 wherein R¹ is —N(R⁸)(R⁹), X is 4-chloro or 5-chloro, Y is6-chloro, Z is hydrogen, and R⁸ and R⁹ are ethyl.
 12. A hydrochloridesalt of the compound of claim
 11. 13. A compound of claim 10 wherein R¹is —N(O)(R¹⁴)(R¹⁵), X is 5-chloro, Y is 6-chloro, Z is hydrogen, and R¹⁴and R¹⁵ are ethyl.
 14. A compound of claim 8 wherein A is Formula III,where Formula III is —(CH₂)_(n)—U—R² III wherein U is O; R² is selectedfrom 1-R⁴, wherein R⁴ is

where X, Y, and Z are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl,alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy; B and D are hydrogen; R isheterocyclyl; where the heterocyclyl moiety may be optionallysubstituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl; and thecorresponding agriculturally acceptable salts thereof.
 15. A compound ofclaim 14 wherein A is Formula III, where Formula III is —(CH₂)_(n)—U—R²III wherein R² is selected from 1-R⁴, wherein R⁴ is

where X, Y, and Z are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl,haloalkyl, nitrilyl, alkenyl, alkoxy, haloalkoxy, carbonyl,alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl,aryl, and aryloxy, where the aryl moieties may be optionally substitutedwith halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy; R is apiperazinyl moiety; where the piperazinyl moiety may be optionallysubstituted with halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,alkoxycarbonyl, aryl, arylcarbonyl, benzyl, allyl, propargyl; and thecorresponding agriculturally acceptable salts thereof.
 16. A compound ofclaim 15 wherein the piperazinyl moiety is substituted with 4-ethyl; Xis 5-chloro, Y is 6-chloro or 6-bromo, and Z is hydrogen.
 17. Acomposition containing an insecticidally effective amount of a compoundof claim 1 in admixture with at least one agriculturally acceptableextender or adjuvant.
 18. A method of controlling insects that comprisesapplying to locus where control is desired an insecticidally effectiveamount of a composition of claim
 17. 19. A compound of formula XII:

wherein: A is —(CH₂)_(n)—U—R² wherein n is 0 or 1; U is —C(O)—, —CH₂—,oxygen, or —NR⁵, where R⁵ is selected from the group consisting ofhydrogen, hydroxy, alkyl, sulfonylalkyl, cabonylamino, andcarbonylalkyl; R² is selected from hydrogen, halo, hydroxy, and 1-R⁴,wherein: R⁴ is

where X, Y, and Z are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl,alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy; R is —T—(CH₂)_(m)—R¹, where T isselected from the group consisting of oxygen, nitrogen, and sulfur; m is0, 1, 2, 3, or 4; R¹ is hydrogen, halo, alkyl, or —N(R⁸)(R⁹); where R⁸and R⁹ are independently selected from the group consisting of hydrogen,alkyl, alkoxy, acetyl, alkoxycarbonyl, alkoxyalkyl, aminoalkyl,carbonylamino, and —(CH₂)_(p)—N(R¹⁶)(R¹⁷), where p is 1 or 2; R¹⁶ andR¹⁷ are independently selected from the group consisting of hydrogen,alkyl, alkoxy, alkoxyalkyl, and aminoalkyl.
 20. A compound of formulaUU:

where X, Y, and Z are independently selected from the group consistingof hydrogen, halogen, cyano, nitro, amino, azido, carboxyl, alkyl,alkynyl, haloalkyl, haloalkylthio, nitrilyl, alkenyl, alkoxy,haloalkoxy, carbonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl,haloalkoxycarbonyl, phenyl, aryl, and aryloxy, where the phenyl and arylmoieties may be optionally substituted with halogen, haloalkyl,haloalkyl, alkoxy, or haloalkoxy; T is selected from the groupconsisting of oxygen, nitrogen, and sulfur; and R¹⁸ is alkyl.